Photosensitive or radiation-sensitive resin composition, photosensitive or radiation-sensitive film, pattern forming method, and method for manufacturing electronic devices.

Abstract

An actinic ray-sensitive or radiation-sensitive resin composition is provided which has excellent storage stability and which enables excellent pattern shapes to be obtained when forming fine patterns (specifically, with a line width or space width less than or equal to 50 nm). This actinic ray-sensitive or radiation-sensitive film is an actinic ray-sensitive or radiation-sensitive resin composition that contains a compound (I) that generates an acid when irradiated by actinic rays or radiation, wherein the aforementioned compound (I) has two or more acid anionic groups and the same number of cationic groups, wherein at least one among the aforementioned acid anionic groups and at least one among the aforementioned cationic groups are linked by a covalent bond, and two or more acid groups generated by the aforementioned compound (I) by irradiation of the actinic rays or radiation include at least two acid groups with different acid dissociation constants (pKa).

Description

[Technical Field]

[0001] The present invention relates to a photosensitive or radiation-sensitive resin composition, a photosensitive or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device. More specifically, the present invention relates to a photosensitive or radiation-sensitive resin composition, a photosensitive or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device, which are suitably used in ultramicrolithography processes applicable to manufacturing processes for ultra-large-scale integrations (ULSIs) and high-capacity microchips, processes for creating molds for nanoimprints, and processes for manufacturing high-density information recording media, as well as other photofabrication processes. [Background technology]

[0002] Traditionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs, microfabrication has been performed using lithography with photoresist compositions. In recent years, with the increasing integration of integrated circuits, there has been a growing demand for the formation of ultrafine patterns in the submicron or quarter-micron region. Accordingly, there has been a trend toward shorter exposure wavelengths, from the g-line to the i-line, and further to KrF excimer laser light. Currently, exposure machines using ArF excimer lasers with a wavelength of 193 nm as the light source have been developed. Furthermore, as a technique to further improve resolution, development of the so-called immersion method has been progressing, in which a high refractive index liquid (hereinafter also called "immersion liquid") is filled between the projection lens and the sample.

[0003] Furthermore, in addition to excimer laser light, lithography using electron beams (EB), X-rays, and extreme ultraviolet (EUV) light is currently under development. Accordingly, chemically amplified resist compositions that are highly sensitive to various types of radiation and exhibit excellent sensitivity and resolution are being developed.

[0004] For example, Patent Documents 1 and 2 describe photosensitive or radiation-sensitive resin compositions containing a compound that generates acid upon irradiation with active light or radiation represented by a specific general formula (Z1). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2013-167825 [Patent Document 2] International Publication No. 2013 / 121819 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] In recent years, patterns have become finer, and there is a need for further improvements in the properties of photosensitive or radiation-sensitive resin compositions used to form such patterns. While the prior art described in Patent Documents 1 and 2 offers excellent performance in terms of sensitivity and other aspects, there was room for further improvement, particularly in the pattern shape of fine patterns.

[0007] Therefore, an object of the present invention is to provide a photosensitive or radiation-sensitive resin composition that has excellent storage stability and can produce excellent pattern shapes when forming fine patterns (especially line width or space width of 50 nm or less). Another object of the present invention is to provide a photosensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device using the above-mentioned photosensitive or radiation-sensitive resin composition. [Means for solving the problem]

[0008] The inventors have found that the above problem can be solved by the following configuration. <1> A photosensitive or radiation-sensitive resin composition containing a compound (I) that generates acid upon irradiation with active light or radiation, The above compound (I) has two or more acid anionic groups and the same number of cationic groups as the above acid anionic groups, At least one of the above acid anionic groups and at least one of the above cationic groups are linked via a covalent bond. The two or more acidic groups generated by irradiation with active light or radiation include at least two acidic groups with different acid dissociation constants (pKa). A photosensitive or radiation-sensitive resin composition in which the above compound (I) is a compound represented by any of the following general formulas (I)-1 to (I)-5.

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[12] below) are also described below.

[0009] [1] A photosensitive or radiation-sensitive resin composition containing a compound (I) that generates acid upon irradiation with active light or radiation, The above compound (I) has two or more acid anionic groups and the same number of cationic groups as the above acid anionic groups, At least one of the above acid anionic groups and at least one of the above cationic groups are linked via a covalent bond. A photosensitive or radiation-sensitive resin composition in which two or more acid groups that generate compound (I) upon irradiation with active light or radiation include at least two acid groups with different acid dissociation constants (pKa).

[0010] [2] The photosensitive or radiation-sensitive resin composition according to [1], wherein compound (I) is a compound in which one cationic group and two acid anionic groups are linked via covalent bonds.

[0011] [3] The photosensitive or radiation-sensitive resin composition according to [1] or [2], wherein the compound (I) is a compound represented by any of the following general formulas (I)-1 to (I)-5.

[0012] [ka]

[0013] In general formulas (I)-1 to (I)-5, A 11 - ~A 20 - Each of these independently represents an acid anionic group. C 11 + ~C 20 + Each of these independently represents a cationic group. L 11 ~L 14 , and L 16 ~L 21 Each of these independently represents a divalent organic group. L 15 This represents a trivalent organic group.

[0014] [4] A in the above general formulas (I)-1 to (I)-5 11 - , A 13 - ~A 16 - , A 18 -The photosensitive or radiation-sensitive resin composition according to [3], wherein each independently represents an acid anionic group represented by the following formula (A-1) or (A-2).

[0015] [ka]

[0016] In the above equations (A-1) to (A-2), R A This represents an organic group. * indicates the connection position.

[0017] [5] A in the above general formulas (I)-1, (I)-4 and (I)-5 12 - , A 17 - , A 19 - , A 20 - The photosensitive or radiation-sensitive resin composition according to [3] or [4], wherein each independently represents an acid anionic group represented by any of the following formulas (B-1) to (B-3).

[0018] [ka]

[0019] In the above equations (B-1) to (B-3), * indicates the connection position.

[0020] [6] A photosensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the difference between the maximum and minimum pKa values ​​of the pKa of two or more acid groups that generate compound (I) upon irradiation with active light or radiation is 1.60 or more. [7] The photosensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the compound (I) is a compound having an ionic structure in which a pair of one of the acid anionic groups and one of the cationic groups are linked via an ionic bond. [8] The photosensitive or radiation-sensitive resin composition according to any one of [1], [3] to [6], wherein compound (I) is a compound in which all of the acid anionic groups and all of the cationic groups are linked via covalent bonds.

[0021] [9] A photosensitive or radiation-sensitive resin composition containing a compound (I) that generates acid upon irradiation with active light or radiation, The above compound (I) has two or more acid anionic groups and the same number of cationic groups as the above acid anionic groups, At least one of the above acid anionic groups and at least one of the above cationic groups are linked via a covalent bond. Two or more acid anionic groups of the above compound (I) include two or more anionic groups selected from the group consisting of the following formulas (C-1) to (C-15). Actinic ray-sensitive or radiation-sensitive resin composition.

[0022] [ka]

[0023] In the above general formulas (C-1) to (C-15), * indicates the connection position. Rf 1 ~Rf 8 Each of these independently represents a fluorine atom or a monovalent substituent containing one or more fluorine atoms. Rf 9 This represents a perfluoroalkyl group. R 1 ~R 7 Each of these independently represents a monovalent substituent that does not contain a hydrogen atom or a fluorine atom. Ar1 ~Ar 4 Each of these independently represents an aromatic ring.

[0024]

[10] A photosensitive or radiation-sensitive film formed from a photosensitive or radiation-sensitive resin composition described in any one of items [1] to [9].

[0025]

[11] A step of forming an active photosensitive or radiation-sensitive film on a substrate using an active photosensitive or radiation-sensitive resin composition described in any one of items [1] to [9], A step of exposing the above-mentioned photosensitive or radiation-sensitive film, A pattern forming method comprising the step of developing the exposed photosensitive or radiation-sensitive film using a developer.

[0026]

[12] A method for manufacturing an electronic device, including the pattern formation method described in

[11] . [Effects of the Invention]

[0027] The present invention provides a photosensitive or radiation-sensitive resin composition that exhibits excellent storage stability and yields excellent pattern shapes in the formation of fine patterns (particularly those with a line width or space width of 50 nm or less). Another objective of the present invention is to provide a photosensitive or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device using the above-mentioned photosensitive or radiation-sensitive resin composition. [Modes for carrying out the invention]

[0028] The present invention will be described in detail below. The following description of the constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, regarding the notation of groups (atomic groups), unless contrary to the spirit of the present invention, notations that do not specify substituted or unsubstituted include both unsubstituted and substituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. Furthermore, in this specification, "organic group" means a group containing at least one carbon atom. Unless otherwise specified, monovalent substituents are preferred.

[0029] In this specification, "active light" or "radiation" means, for example, the emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB). In this specification, "light" means active light or radiation. In this specification, unless otherwise specified, "exposure" includes not only exposure with emission line spectra from mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet light, X-rays, and EUV light, but also drawing with particle beams such as electron beams and ion beams. In this specification, "~" is used to mean that the numbers before and after it are included as the lower and upper limits, respectively.

[0030] In this specification, the bonding direction of the divalent group as expressed is not limited unless otherwise specified. For example, in a compound represented by the formula "XYZ", if Y is -COO-, Y may also be -CO-O- or -O-CO-. Furthermore, the above compound may also be "X-CO-OZ" or "XO-CO-Z".

[0031] In this specification, (meth)acrylate refers to acrylate and methacrylate, and (meth)acrylic refers to acrylic and methacrylic. In this specification, weight-average molecular weight (Mw), number-average molecular weight (Mn), and degree of dispersion (hereinafter also referred to as "molecular weight distribution") (Mw / Mn) are defined as polystyrene-converted values ​​obtained by GPC (Gel Permeation Chromatography) measurement using a GPC (Gel Permeation Chromatography) instrument (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0032] In this specification, the acid dissociation constant (pKa) refers to the pKa in aqueous solution, and specifically, it is a value calculated using the software package 1 described below, based on a database of Hammett substituent constants and known literature values. All pKa values ​​described herein are those calculated using this software package. Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0033] Furthermore, pKa can also be determined by molecular orbital calculations. Specifically, this method involves calculating the H₂ in aqueous solution based on the thermodynamic cycle. + One method is to calculate it by calculating the dissociation free energy. + The dissociation free energy can be calculated using, for example, DFT (Density Functional Theory), but various other methods have been reported in the literature and are not limited to this. Several software programs exist that can perform DFT; for example, Gaussian16 is one such program.

[0034] In this specification, pKa refers to a value calculated using software package 1, based on a database of Hammett substituent constants and publicly available literature values, as described above. However, if pKa cannot be calculated using this method, the value obtained by Gaussian16 based on DFT (Density Functional Theory) shall be adopted. Furthermore, in this specification, pKa refers to "pKa in aqueous solution" as described above, but if pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" shall be used.

[0035] "Solid content" refers to components that form photosensitive or radiation-sensitive films, and does not include solvents. Furthermore, any component that forms a photosensitive or radiation-sensitive film is considered solid content, even if its state is liquid.

[0036] Furthermore, in this specification, there are no particular limitations on the type of substituent, the position of the substituent, or the number of substituents when we say "may have substituents." The number of substituents may be, for example, one, two, three, or more. Examples of substituents include monovalent nonmetallic groups excluding hydrogen atoms, and for example, substituents T can be selected from the following:

[0037] (substituent T) Substituents T include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy; and acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl, and methoxalyl. Examples include alkylsulfanil groups such as methylsulfanil and tert-butylsulfanil; arylsulfanil groups such as phenylsulfanil and p-tolylsulfanil; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; monoalkylamino groups; dialkylamino groups; arylamino groups; and combinations thereof.

[0038] [Actinic ray-sensitive or radiation-sensitive resin composition] The photosensitive or radiation-sensitive resin composition according to the present invention (hereinafter also referred to as "the composition of the present invention") is A photosensitive or radiation-sensitive resin composition containing a compound (I) that generates acid upon irradiation with active light or radiation, The above compound (I) has two or more acid anionic groups and the same number of cationic groups as the above acid anionic groups, At least one of the above acid anionic groups and at least one of the above cationic groups are linked via a covalent bond. The two or more acid groups generated from compound (I) upon irradiation with active light or radiation are a photosensitive or radiation-sensitive resin composition containing at least two acid groups with different acid dissociation constants (pKa).

[0039] Furthermore, the composition of the present invention is a photosensitive or radiation-sensitive resin composition containing a compound (I) that generates acid upon irradiation with active light or radiation. The above compound (I) has two or more acid anionic groups and the same number of cationic groups as the above acid anionic groups, At least one of the above acid anionic groups and at least one of the above cationic groups are linked via a covalent bond. Two or more acid anionic groups of the above compound (I) include two or more anionic groups selected from the group consisting of the following formulas (C-1) to (C-15). It is a photosensitive or radiation-sensitive resin composition.

[0040] [ka]

[0041] In the above general formulas (C-1) to (C-15), * indicates the connection position. Rf 1 ~Rf 8 Each of these independently represents a fluorine atom or a monovalent organic group containing one or more fluorine atoms. Rf 9 This represents a perfluoroalkyl group. R 1 ~R 7 Each of these independently represents a monovalent substituent that does not contain a hydrogen atom or a fluorine atom. Ar 1 ~Ar 4 Each of these independently represents an aromatic ring.

[0042] Because the present invention adopts the above configuration, it has excellent storage stability and can obtain excellent pattern shapes when forming fine patterns (especially line width or space width of 50 nm or less). The reason is not clear, but it is presumed to be as follows. Compound (I) contained in the composition of the present invention can function as a compound that generates the acid necessary for the reaction of the resin in the exposure area, as described later, and as an acid diffusion control agent that traps excess acid generated from the exposure area. As described above, compound (I) has two or more acid anionic groups and the same number of cationic groups as the acid anionic groups, and at least one of the acid anionic groups and at least one of the cationic groups are linked via a covalent bond. In other words, compound (I) has a zwitterionic structure in which a pair of cationic groups and an acid anionic group are covalently linked. This makes the cationic group, which is susceptible to nucleophilic attack, more easily protected by the acid anionic group, allowing the cationic group and other components susceptible to nucleophilic attack to exist stably in compound (I). As a result, compound (I) is less likely to decompose during storage of the composition, and it is presumed that the composition has excellent storage stability.

[0043] Furthermore, in the first composition of the present invention, the two or more acid groups generated from compound (I) by irradiation with active light or radiation include at least two acid groups with different acid dissociation constants (pKa). Since the acid dissociation constants of at least two of the acid groups mentioned above are different, typically, the acid group with a low acid dissociation constant is more likely to become the acid necessary for the resin reaction in the exposed area, while the anionic group corresponding to the acid group with a high acid dissociation constant is more likely to trap excess acid generated from the exposed area. Furthermore, since compound (I) possesses both of the above functions within the same molecule, it is believed that the desired reaction in the exposed area can be carried out with high precision, resulting in excellent pattern shapes even when forming fine patterns (especially line widths or space widths of 50 nm or less). Furthermore, in the second composition of the present invention, as described above, it contains compound (I), and two or more acid anionic groups of compound (I) contain two or more anionic functional groups represented by two or more of the following formulas (C-1) to (C-15). With such a configuration, the two or more acid groups generated from compound (I) by irradiation with active light or radiation can contain at least two acid groups with different acid dissociation constants (pKa). For the same reasons as explained in the first composition, it is considered that an excellent pattern shape can be obtained even when forming fine patterns (especially line width or space width of 50 nm or less).

[0044] Based on the above, it is believed that the present invention provides excellent storage stability for the composition and enables the creation of excellent pattern shapes when forming fine patterns (especially those with a line width or space width of 50 nm or less).

[0045] The composition of the present invention is preferably a resist composition, and may be either a positive-type resist composition or a negative-type resist composition. It may also be a resist composition for alkaline development or a resist composition for organic solvent development. Furthermore, the composition of the present invention is preferably a chemically amplified resist composition, and more preferably a chemically amplified positive resist composition. The resist composition is typically a chemically amplified resist composition.

[0046] The first composition of the present invention is a photosensitive or radiation-sensitive resin composition containing a compound (I) that generates acid upon irradiation with active light or radiation, The above compound (I) has two or more acid anionic groups and the same number of cationic groups as the above acid anionic groups, At least one of the above acid anionic groups and at least one of the above cationic groups are linked via a covalent bond. The two or more acid groups generated from compound (I) upon irradiation with active light or radiation are a photosensitive or radiation-sensitive resin composition containing at least two acid groups with different acid dissociation constants (pKa).

[0047] Furthermore, the second composition of the present invention is a photosensitive or radiation-sensitive resin composition containing a compound (I) that generates acid upon irradiation with active light or radiation, The above compound (I) has two or more acid anionic groups and the same number of cationic groups as the above acid anionic groups, At least one of the above acid anionic groups and at least one of the above cationic groups are linked via a covalent bond. The above compound (I) is a photosensitive or radiation-sensitive resin composition in which two or more acid anionic groups are selected from the group consisting of the following formulas (C-1) to (C-15). In this specification, the compositions of the present invention encompass both the first composition and the second composition of the present invention. In the following, we will first describe in detail the various components of the composition of the present invention.

[0048] <(I) Compounds that generate acid upon irradiation with active light or radiation> As described above, the photosensitive or radiation-sensitive resin composition of the present invention contains compound (I) (also referred to as "compound (I)") which generates acid upon irradiation with active light or radiation. Compound (I) in the first composition of the present invention has two or more acid anionic groups and the same number of cationic groups as the acid anionic groups, and at least one of the acid anionic groups and at least one of the cationic groups are linked via a covalent bond, and the two or more acid groups produced from compound (I) by irradiation with active light or radiation include at least two acid groups with different acid dissociation constants (pKa). In compound (I), at least one of the acid anionic groups and at least one of the cationic groups are linked via a covalent bond. In other words, compound (I) has at least one zwitterionic structure. Here, a "zwitterionic structure" refers to a structure in which a pair of "positively charged functional groups (cationic groups)" and "negatively charged functional groups (anionic groups (specifically acid anionic groups))" are linked by a covalent bond. Furthermore, "via covalent bonding" includes both the case in which the cationic group and the anionic group are bonded by a single bond, and the case in which the cationic group and the anionic group are bonded by a linking group. Compound (I) has two or more acid anionic groups and the same number of cationic groups as the acid anionic groups. In compound (I), two or more acid anionic groups and the same number of cationic groups as the above acid anionic groups may or may not be linked via covalent bonds.

[0049] Furthermore, if two or more acid anionic groups and the same number of cationic groups as the acid anionic groups are not linked by covalent bonds, then compound (I) will have at least one free ionic structure. Here, a free ionic structure, as defined herein, refers to a structure in which a pair of "positively charged functional groups (cationic groups)" and "negatively charged functional groups (anionic groups (specifically acid anionic groups))" form an ionic pair via ionic bonds (without covalent bonds). In this case, the cationic group in the free ionic structure may be covalently linked to the zwitterionic structure, and the acid anionic group in the free ionic structure may be covalently linked to the zwitterionic structure.

[0050] Compound (I) may have one zwitterionic structure or multiple zwitterionic structures, and if it has multiple zwitterionic structures, the multiple zwitterionic structures may be of the same type or of different types. Compound (I) may have one free ionic structure or multiple free ionic structures, and if it has multiple free ionic structures, the multiple free ionic structures may be of the same type or of different types.

[0051] Compound (I) is a compound that generates acid upon irradiation with active light or radiation (a photoacid generator). As described above, when compound (I) is irradiated with active light or radiation, two or more acidic groups produced from compound (I) contain at least two acidic groups with different acid dissociation constants (pKa). "Two or more acidic groups arising from compound (I)" are derived from two or more acid anionic groups and include at least two acidic groups with different acid dissociation constants. Here, "containing at least two acid groups with different acid dissociation constants" is not limited to cases where the acid dissociation constants of two or more acid groups are all different, but also includes cases where some acid groups have the same acid dissociation constant. Specifically, for example, if compound (I) has two acid anionic groups, the two acid groups produced from compound (I) by irradiation with active light or radiation will include two acid groups with different acid dissociation constants (pKa), and the acid dissociation constants of the two acid groups will be different. For example, if compound (I) has three acid anionic groups, the three acid groups produced from compound (I) by irradiation with active light or radiation may all have different acid dissociation constants (pKa), or two of the three acid groups may have the same acid dissociation constant and the remaining one may have a different acid dissociation constant. In the latter case, the three acid groups produced from compound (I) include two acid groups with different acid dissociation constants.

[0052] Here, as described above, when compound (I) is irradiated with active light or radiation, two or more acid groups are generated from compound (I), and each of these acid groups contains at least two acid groups with different acid dissociation constants (pKa). When compound (PI) is irradiated with active light or radiation, two or more acid groups with different pKas are generated, and the resulting compound (PI) has an acid group with relatively strong acidity (acid group 1) and an acid group with relatively weak acidity (acid group 2) within the same compound. Typically, acid group 1 readily reacts with the acid-degradable group in the resin described later, and acid group 2 readily captures excess acid generated in the exposed area and prevents its diffusion to the unexposed area. Therefore, using such a compound (I) is preferable because it allows for a better pattern shape to be achieved.

[0053] The method for determining the pKa of at least two acid groups generated from compound (I) by irradiation with active light or radiation is as follows: (1) Consider replacing all acid anionic groups in compound (I) with corresponding acid groups to produce an acid group-containing compound (PIA). Depending on the structure of compound (I), there are two cases in which an acid group-containing compound (PIA) with multiple acid groups is produced as a single compound (single molecule) (Case A), and cases in which a compound with one or more acid groups is formed as multiple compounds (multiple molecules) (Case B).

[0054] (2) In the case of Case A (specific example being Embodiment 1 below), consider an acid group-containing compound (PIA-1) obtained by converting the acid group with the lowest acid dissociation constant among the multiple acid groups of the acid group-containing compound (PIA) back to its corresponding acid anionic group, determine the pKa when transitioning from the acid group-containing compound (PIA) to the acid group-containing compound (PIA-1), and set this as the pKa of the acid group converted back to the acid anionic group. Next, consider a compound (PIA-2) obtained by converting the acid group with the lowest acid dissociation constant (if there is only one acid group, that acid group) among the one or more acid groups of the acid group-containing compound (PIA-1) back to its corresponding acid anionic group, determine the pKa when transitioning from the acid group-containing compound (PIA-1) to the acid group-containing compound (PIA-2), and set this as the pKa of the acid group converted back to the acid anionic group. By performing this process until all acidic groups are removed from the compound, the pKa of the multiple acidic groups present in the acidic group-containing compound (PIA) can be determined. In the above method, if there are multiple acid groups with the lowest acid dissociation constant, first, one of these acid groups is arbitrarily selected, and the pKa of the transition to the compound (PIA#) in which it has been converted back to the corresponding acid anionic group is determined. The pKa of the remaining (unselected) acid groups is then obtained by determining the pKa of the transition from compound (PIA#) to "the compound (PIA##) in which an acid group further selected from the remaining acid groups has been converted back to the corresponding acid anionic group."

[0055] (3) In the case of Case B (specifically, the embodiment described in Actual 2 below), the pKa of each acid group in a compound (multiple molecules) having one or more acid groups is determined. If there is only one acid group in the compound, the pKa of this acid group is the pKa of the acid group when the acid group in that compound is converted back to the corresponding acid anionic group. If the compound having one or more acid groups is a compound having multiple acid groups, the pKa of each acid group is determined in accordance with the method in (2) above.

[0056] (4) The acid group-containing compound (PIA) contains an iodine cation (I) as a component of the cationic group. + If it contains iodine cation (I + (I + Perform steps (2) and (3) above, using H) as an acid group-containing compound (PIA).

[0057] In the embodiments 1, 2, and examples described later, among the pKa values ​​of multiple acid groups obtained for compound (I), the one with the lowest acid dissociation constant (pKa) is selected and denoted as acid dissociation constant a1 (pKa1), then the one with the next lowest acid dissociation constant is selected and denoted as acid dissociation constant a2 (pKa2), then the one with the next lowest acid dissociation constant is selected and denoted as acid dissociation constant a3 (pKa3), and so on, with the acid dissociation constants being denoted sequentially. In the case of multiple acid groups with the same pKa, one of them should be selected and assigned an acid dissociation constant number. In any case, upon irradiation with active light or radiation, at least two acid groups generated from compound (I) include at least two acid groups with different acid dissociation constants.

[0058] The method for measuring pKa is described below in detail. The acid dissociation constant a1 (first acid dissociation constant) is assumed to be smaller than the acid dissociation constant a2 (second acid dissociation constant).

[0059] (Aspect 1) The following describes a method for measuring the pKa of two acid groups derived from the above compound (I), which consists of one cationic group and two acid anionic groups linked by covalent bonds. The acid anionic group in the above free ionic structure is A1 - , the acid anionic group in the above zwitterionic structure is A2 - (However, A1 - The pKa (acid dissociation constant a1) of the acid group (A1H) derived from this group. <A2 - (Let the pKa (acid dissociation constant a2) of the acid group (A2H) derived from [the source] be the pKa.) A1 - The countercation of the acid anionic group represented by H + Replace with A2 - H + In the compound (PIA) formed by the addition of A1H, the pKa of the group represented by A1H is lower than the pKa of the group represented by A2H. The acid dissociation constants a1 and a2 are determined by the method described above. Furthermore, the cationic group contains an iodine cation (I + ) If present, the form with added hydrogen atoms, I + Let's determine the acid dissociation constant using H. When the acid dissociation constant of compound (PIA) is determined, compound (PIA) (compound PIA is a "compound having HA1 and HA2") is "A1 - The pKa of the compound having HA2 is the acid dissociation constant a1, and the above "A1 - "A compound having HA2" is "A1 - and A2 - The pKa of a compound having the acid dissociation constant a2 is the pKa of the compound. Furthermore, the above compound (PIA) corresponds to an acid generated by irradiating compound (I) with active light or radiation. A1 - The pKa (acid dissociation constant a1) of the acid group (A1H) derived from this group. <A2 - Although it was explained as the pKa (acid dissociation constant a2) of the acid group (A2H) derived from A1 - The pKa (acid dissociation constant X) of the acid group (A1H) derived from A2- In the case of the pKa (acid dissociation constant Y) of the acid group (A2H) derived from , the acid dissociation constant X becomes the above acid dissociation constant a2, and the acid dissociation constant Y becomes the above acid dissociation constant a1. If the structure contains three or more acid anionic groups, the acid dissociation constant can be determined sequentially in the same manner as described above.

[0060] (Aspect 2) The following describes a method for measuring the pKa of two acid groups derived from compound (I) described above, which consists of two cationic groups and one acid anionic group linked by covalent bonds, with one acid anionic group existing as a free anion (not linked to the cationic groups by covalent bonds). In the above free ionic structure, the acid anionic group as a free anion is A1 - , the acid anionic group in the above zwitterionic structure is A2 - (However, A1 - Let the pKa (acid dissociation constant Y) of the acid group (A1H) derived from A2 - (Let the pKa (acid dissociation constant X) be the acid group (A2H) derived from [the source].) The acid dissociation constant Y and the acid dissociation constant Y can be determined by the method described above. Furthermore, in the zwitterionic structure, the cationic group contains an iodine cation (I + ) If present, the form with added hydrogen atoms, I + Let's determine the acid dissociation constant using H. A2 - H + When the acid dissociation constant of the compound (PIA) derived from the above zwitterionic structure, obtained by adding , is determined, the compound (PIIA) (compound PIA corresponds to "compound having HA2") is "A2 - The pKa of a compound having the characteristic is the acid dissociation constant X. A1 - H +When the acid dissociation constant of the compound (PIA) derived from the acid anionic group as the free anion, which is formed by adding the above, is determined, the compound (PIA) (compound PIA corresponds to "compound having HA1") is "A1 - The pKa of a compound having the characteristic is the acid dissociation constant Y. By comparing the acid dissociation constants X and Y, if the acid dissociation constant X is lower than the acid dissociation constant Y, then the acid dissociation constant X becomes the acid dissociation constant a1, and the acid dissociation constant Y becomes the acid dissociation constant a2. In embodiment 2, if a free acid anionic group is present, the acid dissociation constants a1 and a2 are determined by measuring the acid (acid group) derived from the free acid anionic group and the acid group derived from the zwitterionic structure, and comparing their relative magnitudes. Similarly, the acid dissociation constant can be determined for compounds in which the number of cationic groups and acid anionic groups is increased.

[0061] In the pKa of two or more acidic groups generated by irradiation with active light or radiation, the difference between the maximum and minimum pKa values ​​is preferably 0.50 or more, and more preferably 1.60 or more. Furthermore, regarding the pKa of two or more acidic groups generated by irradiation with active light or radiation, there is no particular upper limit to the difference between the maximum and minimum pKa values, but it is usually 14.00 or less, and more preferably 13.00 or less. In the above-mentioned "equal number of cationic groups to the number of acid anionic groups," the cationic groups are cationic groups in a free ionic structure or cationic groups in a zwitterionic structure. In the above-mentioned "number of cationic groups equal to the number of acid anionic groups," the cationic groups have one or more cationic groups in a zwitterionic structure. In the above-mentioned "two or more acid anionic groups," the acid anionic groups are either acid anionic groups in a free ionic structure or acid anionic groups in a zwitterionic structure. In the above-mentioned "two or more acid anionic groups," the acid anionic groups have one or more acid anionic groups in a zwitterionic structure.

[0062] The acid anionic group is not particularly limited, but specifically, it includes an organic group containing an acid anionic group represented by formula (A-1) or (A-2) described below, or an organic group containing an acid anionic group represented by any of formulas (B-1) to (B-3) described below. The acid anionic group may be an acid anionic group represented by the following formula (A-1) or (A-2), or an acid anionic group represented by any of the following formulas (B-1) to (B-3).

[0063] [ka]

[0064] In the above equations (A-1) to (A-2), R A This represents an organic group. * indicates the connection position.

[0065] [ka]

[0066] In the above equations (B-1) to (B-3), * indicates the connection position.

[0067] R A The organic group represented is not particularly limited, but examples include organic groups having 1 to 30 carbon atoms. The organic group is not particularly limited, but preferably includes alkyl groups, cycloalkyl groups, or aryl groups. The alkyl group described above is not particularly limited, but may be linear or branched, and alkyl groups having 1 to 15 carbon atoms are preferred, and alkyl groups having 1 to 10 carbon atoms are more preferred. The cycloalkyl group may be monocyclic or polycyclic, and is not particularly limited, but a cycloalkyl group having 3 to 15 carbon atoms is preferred, and a cycloalkyl group having 3 to 10 carbon atoms is more preferred. The aryl group is not particularly limited, but an aryl group having 6 to 20 carbon atoms is preferred, and an aryl group having 6 to 10 carbon atoms is more preferred. The alkyl, cycloalkyl, and aryl groups mentioned above may have substituents. While not particularly limited, substituent T is one example. Among these, fluorine atoms and cyano groups are preferred.

[0068] The cationic group is not particularly limited, but is typically an organic cationic group, and is preferably a group having a sulfonium cation or an iodonium cation. Examples of the cationic groups mentioned above include the cation represented by formula (ZaI) described below, the cation represented by formula (ZaII) described below, the group represented by formula (ZBI) described below, or the group represented by formula (ZBII) described below, *-S + (R 401 )-*, or *-I + -* is an example. * indicates the connection position. 401 This will be discussed later.

[0069] Compound (I) is formed by covalently linking at least one acid anionic group with at least one cationic group. The number of cationic groups in compound (I) is not particularly limited, but is preferably five or less, and more preferably four or less. Compound (I) is formed by covalently linking at least one acid anionic group with at least one cationic group. The number of acid anionic groups in compound (I) is not particularly limited, but is preferably five or less, and more preferably four or less.

[0070] If compound (I) is a compound in which one or more cationic groups and two or more acid anionic groups are linked by covalent bonds, the number of cationic groups is not particularly limited, but is preferably five or less, and more preferably four or less. If compound (I) is a compound in which one or more cationic groups and two or more acid anionic groups are covalently linked, the number of acid anionic groups is not particularly limited, but is preferably five or less, and more preferably four or less.

[0071] Compound (I) is preferably a compound in which one cationic group and two acid anionic groups are linked by a covalent bond. In the above-mentioned "one cationic group," the cationic group is a cationic group in a zwitterionic structure. In the above-mentioned "two acid anionic groups," one of the acid anionic groups is an acid anionic group in a free ionic structure, and the other is an acid anionic group in a zwitterionic structure.

[0072] The above compound (I) is preferably a compound represented by any of the following general formulas (I)-1 to (I)-5.

[0073] [ka]

[0074] In general formulas (I)-1 to (I)-5, A 11 - ~A 20 - Each of these independently represents an acid anionic group. C 11 + ~C 20 + Each of these independently represents a cationic group. L 11 ~L 14 , and L 16 ~L 21 Each of these independently represents a divalent organic group. L 15 This represents a trivalent organic group.

[0075] A 11 - , A 13 - ~A 16- , A 18 - The acid anionic group is not particularly limited, but examples include the acid anionic group represented by the following formulas (A-1) or (A-2). A in the above general formulas (I)-1 to (I)-5 11 - , A 13 - ~A 16 - , A 18 - Preferably, each of these independently represents an acid anionic group represented by the following formula (A-1) or (A-2).

[0076] [ka] In the above general formulas (A-1) to (A-2), R A This represents an organic group. * indicates the connection position.

[0077] R A The organic group represented is not particularly limited, but examples include organic groups having 1 to 30 carbon atoms. The organic group is not particularly limited, but preferably includes alkyl groups, cycloalkyl groups, or aryl groups. The alkyl group described above is not particularly limited, but may be linear or branched, and alkyl groups having 1 to 15 carbon atoms are preferred, and alkyl groups having 1 to 10 carbon atoms are more preferred. The cycloalkyl group may be monocyclic or polycyclic, and is not particularly limited, but a cycloalkyl group having 3 to 15 carbon atoms is preferred, and a cycloalkyl group having 3 to 10 carbon atoms is more preferred. The aryl group is not particularly limited, but an aryl group having 6 to 20 carbon atoms is preferred, and an aryl group having 6 to 10 carbon atoms is more preferred. The alkyl, cycloalkyl, and aryl groups mentioned above may have substituents. While not particularly limited, substituent T is one example. Among these, fluorine atoms and cyano groups are preferred.

[0078] A12 - , A 17 - , A 19 - , and A 20 - The acid anionic group is not particularly limited, but examples include an acid anionic group represented by any of the following formulas (B-1) to (B-3). A in the above general formulas (I)-1, (I)-4, and (I)-5 12 - , A 17 - , A 19 - , and A 20 - Preferably, each of these independently represents an acid anionic group represented by any of the following formulas (B-1) to (B-3).

[0079] [ka]

[0080] In the above general formulas (B-1) to (B-3), * indicates the connection position.

[0081] C 11 + , C 13 + , C 16 + The cationic group is not particularly limited, but specifically, organic cations are examples. In particular, among the above organic cations, the cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or the cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)") is preferred.

[0082] [ka]

[0083] In the above equation (ZaI), R 201 , R202 , and R 203 Each of these independently represents an organic group. R 201 , R 202 , and R 203 The number of carbon atoms in the organic group is preferably 1 to 30, and more preferably 1 to 20. Also, R 201 ~R 203 Two of these may bond to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. 201 ~R 203 Examples of groups formed by the bonding of two of these include alkylene groups (e.g., butylene and pentylene groups) and -CH2-CH2-O-CH2-CH2-.

[0084] Preferred embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), the organic cation represented by formula (ZaI-3b) (cation (ZaI-3b)), and the organic cation represented by formula (ZaI-4b) (cation (ZaI-4b)), which will be described later.

[0085] First, let's explain the cation (ZaI-1). The cation (ZaI-1) is R in the above formula (ZaI). 201 ~R 203 It is an arylsulfonium cation in which at least one of the groups is an aryl group. Aryl sulfonium cations are R 201 ~R 203 All of them may be aryl groups, or R 201 ~R 203 A portion of the group may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group. Also, R 201 ~R 203 One of them is an aryl group, R 201 ~R 203 The remaining two of these may bond to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. 201 ~R203 Examples of groups formed by the bonding of two of these include alkylene groups (e.g., butylene group, pentylene group, and -CH2-CH2-O-CH2-CH2-) in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group. Examples of arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0086] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, with the phenyl group being more preferred. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl or cycloalkyl group that the arylsulfonium cation may optionally have is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, or cyclohexyl group.

[0087] R 201 ~R 203Preferred substituents that the aryl group, alkyl group, and cycloalkyl group may have are alkyl groups (e.g., C1-C15), cycloalkyl groups (e.g., C3-C15), aryl groups (e.g., C6-C14), alkoxy groups (e.g., C1-C15), cycloalkylalkoxy groups (e.g., C1-C15), halogen atoms (e.g., fluorine and iodine), hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, or phenylthio groups. The above substituents may have further substituents if possible, and it is also preferable that the alkyl group has a halogen atom as a substituent, forming a halogenated alkyl group such as a trifluoromethyl group. Furthermore, it is preferable that the above substituents form an acid-degradable group in any combination. Furthermore, an acid-degradable group is defined as a group that decomposes upon the action of an acid to produce a polar group, and it is preferable that the polar group is protected by a leaving group that is removed upon the action of an acid. The polar group and leaving group are as described above.

[0088] Next, we will explain the cation (ZaI-2). The cation (ZaI-2) is R in formula (ZaI). 201 ~R 203 However, each of these independently represents a cation that is an organic group without an aromatic ring. The term "aromatic ring" also includes aromatic rings that contain heteroatoms. R 201 ~R 203 The number of carbon atoms in the organic group that does not have an aromatic ring is preferably 1 to 30, and more preferably 1 to 20. R 201 ~R 203 The preferred members are, independently, alkyl groups, cycloalkyl groups, allyl groups, or vinyl groups, more preferably linear or branched 2-oxoalkyl groups, 2-oxocycloalkyl groups, or alkoxycarbonylmethyl groups, and even more preferably linear or branched 2-oxoalkyl groups.

[0089] R 201 ~R 203Examples of alkyl and cycloalkyl groups include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, and norbornyl group). R 201 ~R 203 This may be further substituted with a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. Also, R 201 ~R 203 It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0090] Next, we will explain the cation (ZaI-3b). The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0091] [ka]

[0092] In the formula (ZaI-3b), R 1c ~R 5c Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. R 6c and R 7c Each of these independently represents a hydrogen atom, an alkyl group (e.g., a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R x and R yEach of these independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. Also, R 1c ~R 7c , and also, R x and R y It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0093] R 1c ~R 5c Two or more of the following, R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y These elements may bond to each other to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the above-mentioned rings include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterorings, and polycyclic fused rings formed by the combination of two or more of these rings. Examples of rings include 3- to 10-membered rings, with 4- to 8-membered rings being preferred, and 5- or 6-membered rings being more preferred.

[0094] R 1c ~R 5c Two or more of the following, R 6c and R 7c , and R x and R y Examples of groups formed by the bonding of these atoms include alkylene groups such as butylene and pentylene groups. The methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom. R 5c and R 6c , and R 5c and R x The groups formed by the bonding of these elements are preferably single bonds or alkylene groups. Examples of alkylene groups include methylene groups and ethylene groups.

[0095] R 1c ~R 5c , R 6c , R 7c , R x , R y , and also, R 1c ~R 5c Two or more of the following, R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y The rings formed by the bonding of these elements to each other may have substituents.

[0096] Next, we will explain the cation (ZaI-4b). The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0097] [ka]

[0098] In the formula (ZaI-4b), l represents an integer between 0 and 2. r represents an integer between 0 and 8. R 13 This represents a group containing a hydrogen atom, a halogen atom (e.g., a fluorine atom and an iodine atom), a hydroxyl group, an alkyl group, an alkyl halide, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a cycloalkyl group (which may be a cycloalkyl group itself or a group that partially contains a cycloalkyl group). These groups may have substituents. R 14R represents a hydroxyl group, a halogen atom (e.g., a fluorine atom and an iodine atom), an alkyl group, an alkyl halide, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group in part). These groups may have substituents. 14 If multiple instances exist, each independently represents one of the above-mentioned groups, such as a hydroxyl group. R 15 Each of these independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. 15 They may bond to each other to form a ring. Two R 15 When these atoms bond to each other to form a ring, the ring skeleton may contain heteroatoms such as oxygen atoms or nitrogen atoms. In one embodiment, two R 15 It is preferable that the alkyl group is an alkylene group and that they bond to each other to form a ring structure. The alkyl group, cycloalkyl group and naphthyl group and the two R 15 The ring formed by the bonding of these elements may have substituents.

[0099] In equation (ZaI-4b), R 13 , R 14 , and R 15 The alkyl group may be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms. The alkyl group is preferably a methyl group, ethyl group, n-butyl group, or t-butyl group. Also, R 13 ~R 15 , and also, R x and R y It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0100] Next, we will explain equation (ZaII). In formula (ZaII), R 204 and R 205 Each of these independently represents an aryl group, an alkyl group, or a cycloalkyl group. R 204 and R 205 The aryl group is preferably a phenyl group or a naphthyl group, with the phenyl group being more preferred. 204 and R 205 The aryl group may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of heterocycle aryl group skeletons include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. R 204 and R 205 The alkyl and cycloalkyl groups are preferably linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, or norbornyl group).

[0101] R 204 and R 205 The aryl group, alkyl group, and cycloalkyl group may each independently have substituents. 204 and R 205 Examples of substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., 1 to 15 carbon atoms), cycloalkyl groups (e.g., 3 to 15 carbon atoms), aryl groups (e.g., 6 to 15 carbon atoms), alkoxy groups (e.g., 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. 204 and R 205 It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0102] Specific examples of organic cations are shown below, but the present invention is not limited thereto.

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106] C 12 + , C 15 + , C 17 + , C 19 + , C 20 + The cationic group is not particularly limited, but specifically, organic cations can be mentioned. In particular, the organic cation is preferably a group represented by formula (ZBI) or a group represented by formula (ZBII).

[0107] [ka]

[0108] In formulas (ZBI) and (ZBII), R 301 , R 302 and R 303 Each of these independently represents an aryl group, an alkyl group, or a cycloalkyl group. R 301 ~R 302 These atoms may bond to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. * indicates the connection position.

[0109] R 301 , R 302 and R 303 The aryl group is preferably a phenyl group or a naphthyl group, with the phenyl group being more preferred. 301 , R 302 and R 303The aryl group may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of heterocycle aryl group skeletons include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. R 301 , R 302 and R 303 The alkyl and cycloalkyl groups are preferably linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, or norbornyl group).

[0110] R 301 , R 302 and R 303 The aryl group, alkyl group, and cycloalkyl group may each independently have substituents. 301 , R 302 and R 303 Examples of substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., 1 to 15 carbon atoms), cycloalkyl groups (e.g., 3 to 15 carbon atoms), aryl groups (e.g., 6 to 15 carbon atoms), alkoxy groups (e.g., 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. 301 , R 302 and R 303 The substituents can also independently form acid-degradable groups in any combination of substituents, which is preferable. The acid-degradable groups are as described below.

[0111] R 301 ~R 302 The atoms may bond to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. 301 ~R 302 Examples of groups formed by the bonding of two of these include alkylene groups (e.g., butylene and pentylene groups) and -CH2-CH2-O-CH2-CH2-.

[0112] C 14 + , C 18 + The cationic group is not particularly limited, but specifically, *-S + (R 401 )-*, *-I + -* is an example. * indicates the connection position. R 401 This represents an aryl group, an alkyl group, or a cycloalkyl group. R 401 Specific examples of the aryl group, alkyl group, and cycloalkyl group are, respectively, the above R 301 , R 302 and R 303 The same specific examples as those given for aryl groups, alkyl groups, and cycloalkyl groups can be cited, and the preferred ranges are also the same. R 401 The aryl group, alkyl group, and cycloalkyl group may each independently have substituents. 401 Examples of substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., 1 to 15 carbon atoms), cycloalkyl groups (e.g., 3 to 15 carbon atoms), aryl groups (e.g., 6 to 15 carbon atoms), alkoxy groups (e.g., 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. 401 The substituents can also independently form acid-degradable groups in any combination of substituents, which is preferable. The acid-degradable groups are as described below.

[0113] L 11 ~L 14 and L 16 ~L 21 The divalent organic groups are not particularly limited, but include alkylene groups, cycloalkylene groups, aromatic ring groups, aromatic heterocyclic groups, -C(=O)-, -O-, -S(=O)2-, -S-, and divalent linking groups formed by combining several of these. The alkylene group is not particularly limited, but may be linear or branched. A alkylene group having 1 to 20 carbon atoms is preferred, a alkylene group having 1 to 10 carbon atoms is more preferred, and a alkylene group having 1 to 3 carbon atoms is even more preferred. The cycloalkylene group is not particularly limited, but a cycloalkylene group having 3 to 20 carbon atoms is preferred, an alkylene group having 3 to 10 carbon atoms is more preferred, and a cycloalkylene group having 1 to 6 carbon atoms is even more preferred.

[0114] The aromatic ring group is not particularly limited, but may be monocyclic or polycyclic. Aromatic ring groups with 6 to 20 carbon atoms are preferred, aromatic ring groups with 6 to 14 carbon atoms are more preferred, and aromatic ring groups with 6 to 10 carbon atoms are even more preferred. The aromatic heterocyclic group is not particularly limited and may be monocyclic or polycyclic. The aromatic heterocyclic rings constituting the aromatic heterocyclic group are not particularly limited, but examples include thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, and the like. Alkylene groups, cycloalkylene groups, aromatic ring groups, and aromatic heterocyclic groups may have substituents. The substituents are not particularly limited, but examples include the substituent T mentioned above. Fluorine atoms are preferred as substituents.

[0115] Preferred divalent organic groups include alkylene groups, alkylene groups -O-, -O-alkylene groups, alkylene groups -C(=O)O-, alkylene groups -OC(=O)-, alkylene groups -O-alkylene groups, and aromatic ring groups.

[0116] L 15 The trivalent organic group is not particularly limited, but examples include a group obtained by removing one hydrogen atom from a divalent organic group. As for divalent organic groups, the above L 11 ~L 14 and L 16 ~L 21This is similar to a divalent organic group, and the preferred range is also the same.

[0117] A 11 - The countercation of the acid anionic group represented by H + Replace with A 12 - H + In compound PI-1, which is formed by adding A 11 The pKa of the group represented by H (corresponding to the above acid dissociation constant a1) is A 12 It is preferable that the pKa is lower than that of the group represented by H (corresponding to the acid dissociation constant a2 above). A 13 - The countercation of the acid anionic group represented by H + Replace with A 14 - H + In compound PI-2, which is formed by adding A 13 The pKa of the group represented by H (corresponding to the above acid dissociation constant a1) is A 14 It is preferable that the pKa is lower than that of the group represented by H (corresponding to the acid dissociation constant a2 above). A 15 - H + Add A 16 - The countercation of the acid anionic group represented by H + In compound PI-3, which is obtained by substituting A, 15 The pKa of the group represented by H (corresponding to the above acid dissociation constant a1) is A 16 It is preferable that the pKa is lower than that of the group represented by H (corresponding to the acid dissociation constant a2 above).

[0118] A 17 - H + Add A 18- H + In compound PI-4, which is formed by adding A 18 The pKa of the group represented by H (corresponding to the above acid dissociation constant a1) is A 17 It is preferable that the pKa is lower than that of the group represented by H (corresponding to the acid dissociation constant a2 above). A 19 - H + Add A 20 - H + In compound PI-5, which is formed by adding A 19 The pKa of the group represented by H (corresponding to the above acid dissociation constant a1) is A 20 It is preferable that the pKa is lower than that of the group represented by H (corresponding to the acid dissociation constant a2 above).

[0119] Compound (I) is preferably a compound having an ionic structure in which one of the above acid anionic groups and one of the above cationic groups are linked via an ionic bond. The ionic structure is the free ionic structure described above. Compound (I) is preferably a compound in which all of the above acid anionic groups and all of the above cationic groups are linked via covalent bonds. In this case, compound (I) does not have a free ionic structure.

[0120] The compound (I) in the second composition of the present invention has two or more acid anionic groups and the same number of cationic groups as the acid anionic groups, At least one of the above acid anionic groups and at least one of the above cationic groups are linked via a covalent bond. Two or more acid anionic groups of compound (I) above include two or more anionic groups selected from the group consisting of the following formulas (C-1) to (C-15).

[0121] [ka]

[0122] In the above general formulas (C-1) to (C-15), * indicates the connection position. Rf 1 ~Rf 8 Each of these independently represents a fluorine atom or a monovalent substituent containing one or more fluorine atoms. Rf 9 This represents a perfluoroalkyl group. R 1 ~R 7 Each of these independently represents a monovalent substituent that does not contain a hydrogen atom or a fluorine atom. Ar 1 ~Ar 4 Each of these independently represents an aromatic ring.

[0123] Rf 1 ~Rf 8 The monovalent substituent containing a fluorine atom represented by is not particularly limited, but examples include organic groups containing a fluorine atom. The organic group is not particularly limited, but examples include alkyl groups having 1 to 10 carbon atoms, which may be linear or branched. The organic group may also have substituents other than fluorine atoms. Among these, alkyl groups having a fluorine atom are preferred. Rf 9 The perfluoroalkyl group represented by is not particularly limited, but may include perfluoroalkyl groups having 1 to 10 carbon atoms, which may be linear or branched. Examples of perfluoroalkyl groups include the trifluoromethyl group.

[0124] R 1 ~R 7 The monovalent substituent represented by does not contain a fluorine atom, but examples include organic groups that do not contain a fluorine atom. The organic group is not particularly limited, but examples include alkyl groups having 1 to 10 carbon atoms, which may be linear or branched. The organic group may also have substituents other than fluorine atoms. Ar1 ~Ar 4 The aromatic ring represented by can be monocyclic or polycyclic; for example, an aromatic ring with 6 to 30 carbon atoms can be cited. Specific examples of aromatic rings include benzene rings, naphthalene rings, or anthracene rings. Among these, benzene rings are preferred. Ar 1 ~Ar 4 The aromatic ring represented by may have substituents. 2 The aromatic ring represented by is Rf 4 It may have substituents other than Ar 4 The aromatic ring represented by is Rf 8 It may have substituents other than those mentioned above.

[0125] In "two or more types of anionic groups," the "type" corresponds to each of the formulas (C-1) to (C-15). For example, multiple anionic groups with different structures represented by formula (C-1) represent one type of anionic group.

[0126] The above compound (I) is preferably a compound represented by any of the following general formulas (II)-1 to (II)-5.

[0127] [ka]

[0128] In general formula (II)-1, A 111 - This represents a group that can be expressed by any of the above formulas (C-1) to (C-12). A 112 - This represents a group that can be expressed by any of the above formulas (C-13) to (C-15). C 111 + ~C 112 + Each of these independently represents a cationic group. L 111 ~L 112 Each of these independently represents a single bond or a divalent organic group. In general formula (II)-2, A 113 - and A 114 - Each of these independently represents a group that can be expressed in any of the above formulas (C-1) to (C-12). 13 - and A 14 - They are not the same. C 113 + ~C 114 + Each of these independently represents a cationic group. L 113 ~L 114 Each of these independently represents a single bond or a divalent organic group. In general formula (II)-3, A 115 - and A 116 - Each of these independently represents a group that can be expressed in any of the above formulas (C-1) to (C-12). 115 - and A 116 - They are not the same. C 115 + ~C 116 + Each of these independently represents a cationic group. L 115 This represents a trivalent organic group.

[0129] In general formula (II)-4, A 117 - This represents a group that can be expressed by any of the above formulas (C-13) to (C-15). A 118 - This represents a group that can be expressed by any of the above formulas (C-1) to (C-12). C 117 + ~C 118 + Each of these independently represents a cationic group. L 116 ~L 118 Each of these independently represents a single bond or a divalent organic group.

[0130] In general formula (II)-5, A 119 - and A 120 - Each of these independently represents a group that can be expressed in any of the above formulas (C-3) to (C-15). 119 - and A 120 - They are not the same. C 119 + ~C 120 + Each of these independently represents a cationic group. L 119 ~L 121 Each of these independently represents a single bond or a divalent organic group.

[0131] In general formula (II)-1, A 111 - This represents a group that can be expressed by any of the above formulas (C-1) to (C-12). A 112 - This represents a group that can be expressed by any of the above formulas (C-13) to (C-15). C 111 + The cationic group is the above C 11 + , C 13 + , C 16 + Similar cationic groups can be cited, and the preferred range is also similar. C 112 + The cationic group is the above C 12 + , C 15 + , C 17 + , C 19 + , C 20 + Similar cationic groups can be cited, and the preferred range is also similar. L 111 ~L 112The divalent organic groups are not particularly limited, but include alkylene groups, cycloalkylene groups, aromatic ring groups, aromatic heterocyclic groups, -C(=O)-, -O-, -S(=O)2-, -S-, and divalent linking groups formed by combining several of these. The alkylene group is not particularly limited, but may be linear or branched. A alkylene group having 1 to 20 carbon atoms is preferred, a alkylene group having 1 to 10 carbon atoms is more preferred, and a alkylene group having 1 to 3 carbon atoms is even more preferred. The cycloalkylene group is not particularly limited, but a cycloalkylene group having 3 to 20 carbon atoms is preferred, an alkylene group having 3 to 10 carbon atoms is more preferred, and a cycloalkylene group having 1 to 6 carbon atoms is even more preferred.

[0132] The aromatic ring group is not particularly limited, but may be monocyclic or polycyclic. Aromatic ring groups with 6 to 20 carbon atoms are preferred, aromatic ring groups with 6 to 14 carbon atoms are more preferred, and aromatic ring groups with 6 to 10 carbon atoms are even more preferred. The aromatic heterocyclic group is not particularly limited and may be monocyclic or polycyclic. The aromatic heterocyclic rings constituting the aromatic heterocyclic group are not particularly limited, but examples include thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, and the like. Alkylene groups, cycloalkylene groups, aromatic ring groups, and aromatic heterocyclic groups may have substituents. The substituents are not particularly limited, but examples include the substituent T mentioned above. Fluorine atoms are preferred as substituents.

[0133] Preferred divalent organic groups include alkylene groups, alkylene groups -O-, -O-alkylene groups, alkylene groups -C(=O)O-, alkylene groups -OC(=O)-, alkylene groups -O-alkylene groups, and aromatic ring groups.

[0134] In general formula (II)-2, A 113 - and A 114- Each of these independently represents a group that can be expressed in any of the above formulas (C-1) to (C-12). 13 - and A 14 - They are not the same. C 113 + The cationic group is the above C 11 + , C 13 + , C 16 + Similar cationic groups can be cited, and the preferred range is also similar. C 114 + The cationic group is the above C 14 + , C 18 + Similar cationic groups can be cited, and the preferred range is also similar. L 113 ~L 114 As for the divalent organic group, the above L 111 ~L 112 Similar examples of divalent organic groups can be given, and the preferred range is also similar.

[0135] In general formula (II)-3, A 115 - and A 116 - Each of these independently represents a group that can be expressed in any of the above formulas (C-1) to (C-12). 115 - and A 116 - They are not the same. C 115 + The cationic group is the above C 12 + , C 15 + , C 17 + , C 19 + , C 20 +Similar cationic groups can be cited, and the preferred range is also similar. C 116 + The cationic group is the above C 11 + , C 13 + , C 16 + Similar cationic groups can be cited, and the preferred range is also similar. L 115 The trivalent organic group is not particularly limited, but examples include a group obtained by removing one hydrogen atom from a divalent organic group. As for divalent organic groups, the above L 111 ~L 112 This is similar to a divalent organic group, and the preferred range is also the same.

[0136] In general formula (II)-4, A 117 - This represents a group that can be expressed by any of the above formulas (C-13) to (C-15). A 118 - This represents a group that can be expressed by any of the above formulas (C-1) to (C-12). C 117 + The cationic group is the above C 12 + , C 15 + , C 17 + , C 19 + , C 20 + Similar cationic groups can be cited, and the preferred range is also similar. C 118 + The cationic group is the above C 14 + , C 18 + Similar cationic groups can be cited, and the preferred range is also similar. L 116 ~L 118As for the divalent organic group, the above L 111 ~L 112 Similar examples of divalent organic groups can be given, and the preferred range is also similar.

[0137] In general formula (II)-5, A 119 - and A 120 - Each of these independently represents a group that can be expressed in any of the above formulas (C-3) to (C-15). 119 - and A 120 - They are not the same. C 119 + The cationic group is the above C 12 + , C 15 + , C 17 + , C 19 + , C 20 + Similar cationic groups can be cited, and the preferred range is also similar. C 120 + The cationic group is the above C 12 + , C 15 + , C 17 + , C 19 + , C 20 + Similar cationic groups can be cited, and the preferred range is also similar. L 119 ~L 121 As for the divalent organic group, the above L 111 ~L 112 Similar examples of divalent organic groups can be given, and the preferred range is also similar.

[0138] Specific examples of compound (I) are shown below, but the present invention is not limited to these.

[0139] [ka]

[0140] [ka]

[0141] As described above, compound (I) is a photoacid generator and has two anionic groups (preferably acid anionic groups). It can be used both as a photoacid generator that generates the acid necessary for the resin reaction in the exposed area, and as an acid diffusion control agent. When compound (I) is used as a photoacid generator to produce an acid necessary for the reaction of the resin in the exposure area, and is used in combination with compound (CD), which can be used as an acid diffusion control agent as described later, it is preferable that the acid produced from compound (I) is relatively stronger than the acid produced from compound (CD).

[0142] When compound (I) is used as an acid diffusion control agent, it is preferable to use a photoacid generator in combination such that the acid generated by the photoacid generator, which generates the acid necessary for the resin reaction in the exposed area, is relatively stronger than the acid generated by compound (I). If compound (I) has multiple anionic groups, and the acid dissociation constants of the multiple acid groups generated by irradiation with active light or radiation are different, then a single compound will have both a group that becomes a strong acid (functioning as a photoacid generator) and a group that is assumed to be a weak acid relative to the strong acid group (functioning as an acid diffusion controller). In this way, a single compound can function as both a photoacid generator and an acid diffusion controller.

[0143] Compound (I) can be synthesized by reference to known methods. Specific examples of the synthesis of the compound represented by compound (I) are shown in the examples below.

[0144] The molecular weight of compound (I) is preferably 300 to 3000, more preferably 300 to 2000, and even more preferably 300 to 1500.

[0145] Compound (I) may be used alone or in combination of two or more compounds. In the composition of the present invention, the content of compound (I) (total if there are multiple types) is preferably 0.1 to 35% by mass, more preferably 0.5 to 25% by mass, even more preferably 1 to 20% by mass, and particularly preferably 5 to 20% by mass, based on the total solid content of the composition.

[0146] <(A) Resin> The composition of the present invention preferably contains a resin (A) (hereinafter also referred to as "resin (A)") that decomposes upon the action of an acid and increases in polarity. Resin (A) is typically an acid-degradable resin and usually contains groups that decompose and increase in polarity due to the action of acid (hereinafter also referred to as "acid-degradable groups"), and preferably contains repeating units having acid-degradable groups. Therefore, in the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive-type pattern is suitably formed, and when an organic-based developer is used as the developer, a negative-type pattern is suitably formed. In addition to the repeating units having acid-degradable groups described later, repeating units having acid-degradable groups that include unsaturated bonds are also preferred as repeating units having acid-degradable groups.

[0147] (Repeating unit with acid-degradable group) An acid-degradable group is a group that decomposes upon the action of an acid to produce a polar group. Preferably, the acid-degradable group has a structure in which the polar group is protected by a leaving group that is released upon the action of an acid. In other words, resin (A) has repeating units that decompose upon the action of an acid to produce a polar group. Resins having these repeating units become more polar upon the action of an acid, increasing their solubility in alkaline developers and decreasing their solubility in organic solvents. Preferred polar groups are alkali-soluble groups, such as carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, phosphoric acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene groups, and tris(alkylsulfonyl)methylene groups, as well as alcoholic hydroxyl groups. Among these, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups are preferred as polar groups.

[0148] Examples of leaving groups that are removed by the action of an acid include the groups represented by formulas (Y1) to (Y4). Formula (Y1):-C(Rx1)(Rx2)(Rx3) Formula (Y2):-C(=O)OC(Rx1)(Rx2)(Rx3) Formula (Y3):-C(R 36 )(R 37 )(OR 38 ) Formula (Y4):-C(Rn)(H)(Ar)

[0149] In formulas (Y1) and (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). When all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. In particular, it is preferable that Rx1 to Rx3 each independently represent a linear or branched alkyl group, and it is more preferable that Rx1 to Rx3 each independently represent a linear alkyl group. Two of Rx1 to Rx3 may combine to form a monocycle or polycycle. The alkyl groups Rx1 to Rx3 are preferably C1 to C5 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. The cycloalkyl groups Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The aryl groups Rx1 to Rx3 are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl groups, naphthyl groups, and anthyl groups. Vinyl groups are preferred for the alkenyl groups Rx1 to Rx3. A cycloalkyl group is preferred as the ring formed by the bonding of two Rx1 to Rx3. The cycloalkyl group formed by the bonding of two Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. In cycloalkyl groups formed by the bonding of two Rx1 to Rx3, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with vinylene groups. The group represented by formula (Y1) or formula (Y2) is preferably such that, for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the cycloalkyl group described above. If the resist composition is, for example, an EUV lithography resist composition, it is preferable that the alkyl group, cycloalkyl group, alkenyl group, aryl group represented by Rx1 to Rx3, and the ring formed by the bonding of two Rx1 to Rx3, further have a fluorine atom or an iodine atom as a substituent.

[0150] In formula (Y3), R 36 ~R 38 Each of these independently represents a hydrogen atom or a monovalent organic group. 37 and R 38 These may bond to each other to form a ring. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. 36 It is also preferable that it be a hydrogen atom. Furthermore, the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups mentioned above may include groups containing heteroatoms such as oxygen atoms and / or carbonyl groups. For example, in the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups mentioned above, one or more methylene groups may be replaced with groups containing heteroatoms such as oxygen atoms and / or carbonyl groups. Also, R 38 It may bond with other substituents on the repeating main chain to form a ring. 38 The group formed by the bonding of this molecule with another substituent on the repeating main chain is preferably an alkylene group such as a methylene group. If the resist composition is, for example, a resist composition for EUV lithography, then R 36 ~R 38 A monovalent organic group represented by, and R 37 and R 38 The ring formed by the bonding of these elements may further preferably have a fluorine atom or an iodine atom as a substituent.

[0151] The group represented by formula (Y3-1) below is preferred for formula (Y3).

[0152] [ka]

[0153] Here, L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group which may contain a heteroatom, an ammonium group which may contain a heteroatom, a mercapto group which may contain a cyano group which may contain an aldehyde group which may contain a heteroatom, or a group which is a combination thereof (for example, a group which is a combination of an alkyl group and a cycloalkyl group). Alkyl and cycloalkyl groups may have, for example, one of their methylene groups replaced by a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group. Preferably, one of L1 and L2 is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining an alkylene group and an aryl group. At least two of Q, M, and L1 may be joined to form a ring (preferably a 5-membered or 6-membered ring). In terms of pattern refinement, L2 is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl groups, while examples of tertiary alkyl groups include tert-butyl and adamantane groups. In these embodiments, the glass transition temperature (Tg) and activation energy are increased, which ensures film strength and suppresses fogging.

[0154] If the composition of the present invention is, for example, a photosensitive or radiation-sensitive resin composition for EUV exposure, it is also preferable that the alkyl group, cycloalkyl group, aryl group, and combinations thereof represented by L1 and L2 further have a fluorine atom or an iodine atom as a substituent. Furthermore, it is also preferable that the alkyl group, cycloalkyl group, aryl group, and aralkyl group contain a heteroatom such as an oxygen atom in addition to a fluorine atom and an iodine atom (that is, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, for example, one of the methylene groups is replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group). Furthermore, if the composition of the present invention is, for example, an EUV lithography resist composition, it is also preferable that the heteroatom in the alkyl group which may contain a heteroatom represented by Q, the cycloalkyl group which may contain a heteroatom, the aryl group which may contain a heteroatom, the amino group which may contain a heteroatom, the ammonium group which may contain a heteroatom, the mercapto group which may contain a cyano group which may contain an aldehyde group which may contain a heteroatom, and the group which may contain a heteroatom, is a heteroatom selected from the group consisting of a fluorine atom which may contain a iodine atom which may contain an oxygen atom which may contain a heteroatom.

[0155] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may bond to each other to form a non-aromatic ring. An aryl group is preferred as Ar. If the composition of the present invention is, for example, a resist composition for EUV lithography, it is also preferable that the aromatic ring group represented by Ar, and the alkyl, cycloalkyl, and aryl groups represented by Rn, have a fluorine atom or an iodine atom as a substituent.

[0156] From the standpoint of excellent acid decomposition properties of repeating units, in the case of a leaving group that protects a polar group, if a non-aromatic ring is directly bonded to the polar group (or its residue), it is preferable that the ring member atoms in the non-aromatic ring adjacent to the ring member atom directly bonded to the polar group (or its residue) do not have halogen atoms such as fluorine atoms as substituents.

[0157] Other leaving groups that are removed by the action of an acid may include a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.

[0158] As a repeating unit having an acid-degradable group, the repeating unit represented by formula (A) is also preferred.

[0159] [ka]

[0160] L1 represents a divalent linking group which may have a fluorine atom or an iodine atom; R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom; and R2 represents a leaving group which is eliminated by the action of an acid and which may have a fluorine atom or an iodine atom. However, at least one of L1, R1, and R2 has a fluorine atom or an iodine atom. L1 represents a divalent linking group which may have a fluorine atom or an iodine atom. Examples of divalent linking groups which may have a fluorine atom or an iodine atom include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups which may have a fluorine atom or an iodine atom (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, and arylene groups, etc.), and linking groups formed by linking multiple of these. In particular, L1 is preferably -CO-, an arylene group, or an arylene group-an alkylene group having a fluorine atom or an iodine atom-, and more preferably -CO-, or an arylene group-an alkylene group having a fluorine atom or an iodine atom-. A phenylene group is preferred as the arylene group. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. The total number of fluorine atoms and iodine atoms contained in an alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0161] R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. The total number of fluorine atoms and iodine atoms contained in an alkyl group having a fluorine atom or an iodine atom is not particularly limited, but it is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group described above may also contain heteroatoms other than halogen atoms, such as oxygen atoms.

[0162] R2 represents a leaving group that is eliminated by the action of an acid and may contain a fluorine atom or an iodine atom. Examples of leaving groups that may contain a fluorine atom or an iodine atom include those represented by the above formulas (Y1) to (Y4) and that contain a fluorine atom or an iodine atom.

[0163] As a repeating unit having an acid-degradable group, a repeating unit represented by formula (AI) is also preferred.

[0164] [ka]

[0165] In formula (AI), Xa1 represents a hydrogen atom or an optionally substituted alkyl group. T represents a single bond or a divalent linking group. Rx1 to Rx3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). However, if all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. Two of Rx1 to Rx3 may bond together to form a monocyclic or polycyclic (such as a monocyclic or polycyclic cycloalkyl group).

[0166] Examples of alkyl groups that may have substituents, represented by Xa1, include a methyl group or a -CH2-R 11 The group represented by R is an example. 11 Xa1 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Examples include alkyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, acyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with a halogen atom. Alkyl groups having 3 or fewer carbon atoms are preferred, and methyl groups are more preferred. Xa1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0167] Examples of divalent linking groups for T include alkylene groups, aromatic ring groups, -COO-Rt- groups, and -O-Rt- groups. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0168] The alkyl groups Rx1 to Rx3 are preferably C1 to C4 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. The cycloalkyl groups Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The aryl groups Rx1 to Rx3 are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl groups, naphthyl groups, and anthyl groups. Vinyl groups are preferred for the alkenyl groups Rx1 to Rx3. The cycloalkyl group formed by the bonding of two Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group. Polycyclic cycloalkyl groups such as a norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group are also preferred. Among these, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred. In a cycloalkyl group formed by the bonding of two Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by vinylene groups. The repeating unit represented by formula (AI) preferably has, for example, Rx1 being a methyl group or an ethyl group, and Rx2 and Rx3 being bonded to form the cycloalkyl group described above.

[0169] When each of the above groups has substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0170] The repeating unit represented by formula (AI) is preferably an acid-degradable (meth)acrylate tertiary alkyl ester repeating unit (a repeating unit in which Xa1 represents a hydrogen atom or a methyl group, and T represents a single bond).

[0171] Specific examples of repeating units having acid-degradable groups are shown below, but the present invention is not limited thereto. In the formula, Xa1 represents H, CH3, CF3, or CH2OH, and Rxa and Rxb each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms.

[0172] [ka]

[0173] [ka]

[0174] [ka]

[0175] [ka]

[0176] [ka]

[0177] Resin (A) may have repeating units having acid-degradable groups, including repeating units having acid-degradable groups containing unsaturated bonds. As a repeating unit having an acid-degradable group containing an unsaturated bond, the repeating unit represented by formula (B) is preferred.

[0178] [ka]

[0179] In formula (B), Xb represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group. L represents a single bond or an optionally substituted divalent linking group. Ry1 to Ry3 each independently represent a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group. However, at least one of Ry1 to Ry3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. Two of the Ry1-Ry3 groups may bond to form a monocyclic or polycyclic group (such as a monocyclic or polycyclic cycloalkyl group or cycloalkenyl group).

[0180] Examples of alkyl groups that may have substituents, represented by Xb, include a methyl group or a -CH2-R 11 The group represented by R is an example. 11 Xb represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Examples include alkyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, acyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with a halogen atom. Alkyl groups having 3 or fewer carbon atoms are preferred, and methyl groups are more preferred. Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0181] Examples of divalent linking groups for L include -Rt-, -CO-, -COO-Rt-, -COO-Rt-CO-, -Rt-CO-, and -O-Rt-. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, with an aromatic ring group being preferred. L is preferably a -Rt- group, a -CO- group, a -COO-Rt-CO- group, or a -Rt-CO- group. Rt may have substituents such as a halogen atom, a hydroxyl group, or an alkoxy group. An aromatic group is preferred.

[0182] The alkyl groups Ry1 to Ry3 are preferably C1 to C4 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. The cycloalkyl groups Ry1 to Ry3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The aryl groups Ry1 to Ry3 are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl groups, naphthyl groups, and anthyl groups. A vinyl group is preferred as the alkenyl group for Ry1 to Ry3. An ethynyl group is preferred as the alkynyl group for Ry1 to Ry3. For the cycloalkenyl groups of Ry1 to Ry3, structures containing a double bond in part of a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group are preferred. The cycloalkyl group formed by the bonding of two Ry1 to Ry3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. A cycloalkyl group or cycloalkenyl group formed by the bonding of two Ry1 to Ry3 may have, for example, one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a carbonyl group, a group containing heteroatoms such as -SO2- and -SO3- groups, a vinylidene group, or a combination thereof. Furthermore, in these cycloalkyl groups or cycloalkenyl groups, one or more of the ethylene groups constituting the cycloalkane ring or cycloalkene ring may be replaced by a vinylene group. In the repeating unit represented by formula (B), it is preferable that, for example, Ry1 is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group, and Ry2 and Rx3 are bonded to form the above-mentioned cycloalkyl group or cycloalkenyl group.

[0183] When each of the above groups has substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0184] The repeating units represented by formula (B) are preferably acid-degradable (meth)acrylic acid tertiary ester repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a -CO- group), acid-degradable hydroxystyrene tertiary alkyl ether repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), or acid-degradable styrene carboxylic acid tertiary ester repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (where Rt is an aromatic group)).

[0185] The content of repeating units having acid-degradable groups containing unsaturated bonds is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 80 mol% or less, more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0186] Specific examples of repeating units having an acid-degradable group containing an unsaturated bond are shown below, but the present invention is not limited thereto. In the formula, Xb and L1 represent any of the substituents or linking groups described above, Ar represents an aromatic group, R represents a substituent such as a hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group, hydroxyl group, alkoxy group, acyloxy group, cyano group, nitro group, amino group, halogen atom, ester group (-OCOR''' or -COOR''':R''' is an alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms), or carboxyl group, R' represents a linear or branched alkyl group, monocyclic or polycyclic cycloalkyl group, alkenyl group, alkynyl group, or monocyclic or polycyclic aryl group, Q represents a heteroatom such as an oxygen atom, a carbonyl group, a group containing a heteroatom such as a -SO2- group or -SO3- group, a vinylidene group, or a combination thereof, and n and m represent integers of 0 or more.

[0187] [ka]

[0188] [ka]

[0189] [ka]

[0190] [ka]

[0191] Resin (A) may contain one type of repeating unit having an acid-degradable group, or two or more types in combination. The content of repeating units having acid-degradable groups is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0192] The resin (A) may contain at least one repeating unit selected from the group consisting of group A below, and / or at least one repeating unit selected from the group consisting of group B below. Group A: A group consisting of the following repeating units (20) to (29). (20) Repeating units having an acid group, as described later (21) Repeating units having a fluorine atom, a bromine atom, or an iodine atom, which are described later and do not have either an acid-degradable group or an acid group. (22) Repeating units having a lactone group, a sultone group, or a carbonate group, as described later (23) Repeating units having photoacid generators, as described later (24) Repeating units represented by formula (V-1) or formula (V-2) below, as described later. (25) Repeating units represented by formula (A), as described later (26) Repeating units represented by formula (B), which will be described later (27) Repeating units represented by formula (C), as described later (28) Repeating units represented by formula (D), which will be described later (29) Repeating units represented by formula (E), which will be described later Group B: A group consisting of the following repeating units (30) to (32). (30) Repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups, as described later. (31) Repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition, as described later. (32) Repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group, as described later.

[0193] The resin (A) preferably has acidic groups, and more preferably contains repeating units having acidic groups, as will be described later. The definition of acidic groups will be explained later, along with preferred embodiments of the repeating units having acidic groups. When resin (A) has acidic groups, the interaction between resin (A) and the acid generated from the photoacid generator is improved. As a result, acid diffusion is further suppressed, and the cross-sectional shape of the formed pattern can become more rectangular.

[0194] When the composition of the present invention is used as an activated photosensitive or radiation-sensitive resin composition for EUV, it is preferable that the resin (A) has at least one repeating unit selected from the group consisting of group A. Furthermore, when the composition of the present invention is used as an EUV-sensitive photosensitive or radiation-sensitive resin composition, it is preferable that resin (A) contains at least one of a fluorine atom and an iodine atom. If resin (A) contains both a fluorine atom and an iodine atom, resin (A) may have one repeating unit containing both a fluorine atom and an iodine atom, or resin (A) may contain two types of repeating units: one containing a fluorine atom and another containing an iodine atom. Furthermore, when the composition of the present invention is used as an EUV-sensitive photosensitive or radiation-sensitive resin composition, it is also preferable that the resin (A) has repeating units having aromatic groups. When the composition of the present invention is used as an active photosensitive or radiation-sensitive resin composition for ArF, it is preferable that the resin (A) has at least one repeating unit selected from the group consisting of group B described above. Furthermore, when the composition of the present invention is used as an activated photosensitive or radiation-sensitive resin composition for ArF, it is preferable that resin (A) does not contain either fluorine atoms or silicon atoms. Furthermore, when the composition of the present invention is used as an active photosensitive or radiation-sensitive resin composition for ArF, it is preferable that resin (A) does not have aromatic groups.

[0195] (Repeating units containing acidic groups) The resin (A) may have repeating units having acidic groups. As for the acid group, an acid group with a pKa of 13 or less is preferred. The acid dissociation constant of the above acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10. When resin (A) has acid groups with a pKa of 13 or less, the content of acid groups in resin (A) is not particularly limited, but is often between 0.2 and 6.0 mmol / g. Among these, 0.8 to 6.0 mmol / g is preferred, 1.2 to 5.0 mmol / g is more preferred, and 1.6 to 4.0 mmol / g is even more preferred. If the acid group content is within the above range, development proceeds smoothly, the resulting pattern shape is excellent, and the resolution is also excellent. Preferred acid groups include, for example, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonic acid groups, sulfonamide groups, or isopropanol groups. Furthermore, one or more fluorine atoms (preferably 1 to 2) of the hexafluoroisopropanol group may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). The acid group thus formed, -C(CF3)(OH)-CF2-, is also preferred. Alternatively, one or more fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF3)(OH)-CF2-. The repeating unit having an acidic group is preferably different from the repeating unit having a structure in which a polar group is protected by a leaving group that is removed by the action of the acid described above, and from the repeating unit having a lactone group, sultone group, or carbonate group described later. The repeating unit having an acidic group may also have a fluorine atom or an iodine atom.

[0196] Examples of repeating units having an acidic group include the following:

[0197] [ka]

[0198] As a repeating unit having an acid group, the repeating unit represented by the following formula (1) is preferred.

[0199] [ka]

[0200] In formula (1), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group. R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group, and if there are multiple Rs, they may be the same or different. If there are multiple Rs, they may cooperate to form a ring. A hydrogen atom is preferred as R. a represents an integer from 1 to 3. b represents an integer from 0 to (5-a).

[0201] The following are examples of repeating units having an acid group. In the formulas, a represents 1 or 2.

[0202] [ka]

[0203] [ka]

[0204] [ka]

[0205] [ka]

[0206] Of the repeating units described above, the repeating units specifically described below are preferred. In the formula, R represents a hydrogen atom or a methyl group, and a represents 2 or 3.

[0207] [ka]

[0208] [ka]

[0209] The content of repeating units having acid groups is preferably 10 mol% or more, and more preferably 15 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0210] (A repeating unit that does not possess either an acid-degradable group or an acidic group, but has a fluorine atom, a bromine atom, or an iodine atom.) Resin (A) may have repeating units (hereinafter also referred to as unit X) that do not have either an acid-degradable group or an acid group, but have a fluorine atom, a bromine atom, or an iodine atom, in addition to the <repeating units having an acid-degradable group> and <repeating units having an acid group> described above. Furthermore, it is preferable that the <repeating units having either an acid-degradable group or an acid group, but having a fluorine atom, a bromine atom, or an iodine atom> referred to here are different from other types of repeating units belonging to group A, such as the <repeating units having a lactone group, a sultone group, or a carbonate group> and <repeating units having a photoacid-generating group> described later.

[0211] The repeating unit X is preferably represented by formula (C).

[0212] [ka]

[0213] L5 represents a single bond or an ester group. R9 represents an alkyl group which may have a hydrogen atom, a fluorine atom, or an iodine atom. 10This represents an alkyl group which may have a hydrogen atom, a fluorine atom, or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group which is a combination thereof.

[0214] Examples of repeating units having fluorine or iodine atoms are shown below.

[0215] [ka]

[0216] The content of unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, relative to the total repeating units in resin (A).

[0217] The total content of repeating units in resin (A) that contain at least one of fluorine, bromine, and iodine atoms is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and particularly preferably 40 mol% or more, relative to the total repeating units of resin (A). There is no particular upper limit, but for example, it is 100 mol% or less relative to the total repeating units of resin (A). Examples of repeating units containing at least one of a fluorine atom, a bromine atom, and an iodine atom include a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and having an acid-degradable group, a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and having an acidic group, and a repeating unit having a fluorine atom, a bromine atom, or an iodine atom.

[0218] (Repeating units having a lactone group, sultone group, or carbonate group) The resin (A) may have repeating units (hereinafter also referred to as "unit Y") having at least one selected from the group consisting of lactone groups, sultone groups, and carbonate groups. It is also preferable that unit Y does not have acidic groups such as hydroxyl groups and hexafluoropropanol groups.

[0219] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5-7 membered ring lactone structure or a 5-7 membered ring sultone structure. In particular, a structure in which another ring structure is fused to a 5-7 membered ring lactone structure in the form of a bicyclo or spiro structure, or a structure in which another ring structure is fused to a 5-7 membered ring sultone structure in the form of a bicyclo or spiro structure, is more preferable. The resin (A) preferably has repeating units having lactone groups or sultone groups obtained by abstracting one or more hydrogen atoms from ring member atoms of a lactone structure represented by any of the following formulas (LC1-1) to (LC1-21), or a sultone structure represented by any of the following formulas (SL1-1) to (SL1-3). Furthermore, lactone groups or sultone groups may be directly bonded to the main chain. For example, ring member atoms of lactone groups or sultone groups may constitute the main chain of resin (A).

[0220] [ka]

[0221] The above lactone or sultone structure may have substituents (Rb2). Preferred substituents (Rb2) include C1-C8 alkyl groups, C4-C7 cycloalkyl groups, C1-C8 alkoxy groups, C1-C8 alkoxycarbonyl groups, carboxyl groups, halogen atoms, cyano groups, and acid-degradable groups. n2 represents an integer from 0 to 4. When n2 is 2 or greater, the multiple Rb2 groups may be different, and the multiple Rb2 groups may bond to each other to form a ring.

[0222] Examples of repeating units having a lactone structure represented by any of the formulas (LC1-1) to (LC1-21), or a sultone structure represented by any of the formulas (SL1-1) to (SL1-3), include the repeating unit represented by the following formula (AI).

[0223] [ka]

[0224] In formula (AI), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group of Rb0 may have include a hydroxyl group and a halogen atom. Examples of halogen atoms for Rb0 include fluorine, chlorine, bromine, and iodine. Rb0 is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group combining these. Among these, a single bond or a linking group represented as -Ab1-CO2- is preferred for Ab. Ab1 is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, ethylene group, cyclohexylene group, adamantylene group, or norbornylene group. V represents a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any of the formulas (LC1-1) to (LC1-21), or a group obtained by removing one hydrogen atom from a ring member atom of a sultone structure represented by any of the formulas (SL1-1) to (SL1-3).

[0225] If optical isomers exist for a repeating unit having a lactone group or a sultone group, either optical isomer may be used. Furthermore, one optical isomer may be used alone, or multiple optical isomers may be used in mixture form. When primarily using one optical isomer, its optical purity (ee) is preferably 90 or higher, and more preferably 95 or higher.

[0226] A cyclic carbonate ester group is preferred as the carbonate group. As a repeating unit having a cyclic carbonate ester group, the repeating unit represented by the following formula (A-1) is preferred.

[0227] [ka]

[0228] In formula (A-1), R A 1 R represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group). n represents an integer of 0 or greater. A 2 represents a substituent. If n is 2 or greater, there are multiple R A 2 These may be the same or different. A represents a single bond or a divalent linking group. Preferred divalent linking groups include alkylene groups, divalent linking groups having a monocyclic or polycyclic alicyclic hydrocarbon structure, ether groups, ester groups, carbonyl groups, carboxyl groups, or divalent groups that are combinations thereof. Z represents an atomic group that forms a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

[0229] The unit Y is exemplified below.

[0230] [ka]

[0231] [ka]

[0232] [ka]

[0233] The content of unit Y is preferably 1 mol% or more, and more preferably 10 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 85 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0234] (Repeating unit with photoacid-generating group) The resin (A) may also have repeating units other than those described above, which include a group that generates acid upon irradiation with active light or radiation (hereinafter also referred to as a "photoacid generating group"). An example of a repeating unit having a photoacid-generating group is the repeating unit represented by formula (4).

[0235] [ka]

[0236] R 41 L represents a hydrogen atom or a methyl group. 41 L represents a single bond or a divalent linking group. 42 R represents a divalent linking group. 40 This represents a structural site that decomposes upon irradiation with active light or radiation, generating acid in the side chain. Examples of repeating units having a photoacid-generating group are shown below.

[0237] [ka] JPEG0007853983000059.jpg5857

[0238] Other examples of repeating units represented by formula (4) include the repeating units described in paragraphs

[0094] to

[0105] of Japanese Patent Publication No. 2014-041327, and the repeating units described in paragraph

[0094] of International Publication No. 2018 / 193954.

[0239] The content of repeating units having photoacid generating groups is preferably 1 mol% or more, and more preferably 5 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, relative to the total repeating units in resin (A).

[0240] (The repeating unit is represented by formula (V-1) or formula (V-2) below) The resin (A) may have repeating units represented by the following formula (V-1) or the following formula (V-2). It is preferable that the repeating units represented by the following formulas (V-1) and (V-2) are different from the repeating units described above.

[0241] [ka]

[0242] During the ceremony, R6 and R7 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group. Linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms are preferred as the alkyl group. n3 represents an integer between 0 and 6. n4 represents an integer between 0 and 4. X 4 This is a methylene group, an oxygen atom, or a sulfur atom. Examples of repeating units represented by formula (V-1) or (V-2) are shown below. Examples of repeating units represented by formula (V-1) or (V-2) include the repeating units described in paragraph

[0100] of International Publication No. 2018 / 193954.

[0243] (A repeating unit that reduces the mobility of the main chain) Resin (A) is preferable to have a high glass transition temperature (Tg) in order to suppress excessive diffusion of generated acid or pattern collapse during development. The Tg is preferably greater than 90°C, more preferably greater than 100°C, even more preferably greater than 110°C, and particularly preferably greater than 125°C. Furthermore, in order to have a good dissolution rate in the developer, the Tg is preferably 400°C or lower, and more preferably 350°C or lower. In this specification, the glass transition temperature (Tg) of a polymer such as resin (A) (hereinafter referred to as "Tg of the repeating unit") is calculated by the following method. First, the Tg of each homopolymer consisting only of each repeating unit contained in the polymer is calculated using the Bicerano method. Next, the mass percentage (%) of each repeating unit relative to the total number of repeating units in the polymer is calculated. Then, the Tg for each mass percentage is calculated using Fox's formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed up to obtain the polymer's Tg (°C). The Bicerano method is described in *Prediction of polymer properties*, Marcel Dekker Inc, New York (1993). Furthermore, the calculation of Tg using the Bicerano method can be performed using the polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0244] To increase the Tg of resin (A) (preferably to make the Tg greater than 90°C), it is preferable to reduce the mobility of the main chain of resin (A). Methods for reducing the mobility of the main chain of resin (A) include the following methods (a) to (e). (a) Introduction of bulky substituents into the main chain (b) Introduction of multiple substituents into the main chain (c) Introduction of substituents that induce interactions between resins (A) near the main chain (d) Main chain formation in a cyclic structure (e) Linking of annular structures to the main chain Furthermore, it is preferable that resin (A) has repeating units in which the Tg of the homopolymer is 130°C or higher. Furthermore, there are no particular restrictions on the type of repeating units that exhibit a homopolymer Tg of 130°C or higher; any repeating unit whose homopolymer Tg calculated by the Bicerano method is 130°C or higher is acceptable. Note that depending on the type of functional group in the repeating units represented by formulas (A) to (E) described later, some repeating units may exhibit a homopolymer Tg of 130°C or higher.

[0245] One example of a specific means of achieving (a) above is to introduce repeating units represented by formula (A) into resin (A).

[0246] [ka]

[0247] Formula (A), R A R represents a group containing a polycyclic structure. x represents a hydrogen atom, a methyl group, or an ethyl group. A group containing a polycyclic structure is a group containing multiple ring structures, which may or may not be condensed. Specific examples of repeating units represented by formula (A) are those described in paragraphs

[0107] to

[0119] of International Publication No. 2018 / 193954.

[0248] One example of a specific means of achieving (b) above is to introduce repeating units represented by formula (B) into resin (A).

[0249] [ka]

[0250] In formula (B), R b1 ~R b4 Each of these independently represents a hydrogen atom or an organic group, and R b1 ~R b4 At least two of these represent organic groups. Furthermore, if at least one of the organic groups is a group in which a ring structure is directly linked to the main chain in the repeating unit, the types of other organic groups are not particularly limited. Furthermore, if none of the organic groups are directly linked to the main chain in the repeating unit, then at least two of the organic groups are substituents with three or more constituent atoms excluding hydrogen atoms. Specific examples of repeating units represented by formula (B) are those described in paragraphs

[0113] to

[0115] of International Publication No. 2018 / 193954.

[0251] One example of a specific means of achieving (c) above is to introduce repeating units represented by formula (C) into resin (A).

[0252] [ka]

[0253] In formula (C), R c1 ~R c4 Each of these independently represents a hydrogen atom or an organic group, and R c1 ~R c4 At least one of these groups contains hydrogen-bonding hydrogen atoms within three atoms of the main chain carbon. In particular, it is preferable to have hydrogen-bonding hydrogen atoms within two atoms (closer to the main chain) in order to induce interactions between the main chains of resin (A). Specific examples of repeating units represented by formula (C) are those described in paragraphs

[0119] to

[0121] of International Publication No. 2018 / 193954.

[0254] One example of a specific means of achieving (d) above is to introduce repeating units represented by formula (D) into resin (A).

[0255] [ka]

[0256] In formula (D), "cyclic" refers to a group that forms the main chain in a cyclic structure. The number of constituent atoms in the ring is not particularly limited. Specific examples of repeating units represented by formula (D) are those described in paragraphs

[0126] to

[0127] of International Publication No. 2018 / 193954.

[0257] One example of a specific means of achieving (e) above is to introduce repeating units represented by formula (E) into resin (A).

[0258] [ka]

[0259] In formula (E), Re independently represents either a hydrogen atom or an organic group. Examples of organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups, which may have substituents. A "cyclic" group is a cyclic group that includes carbon atoms in its main chain. There are no particular restrictions on the number of atoms that can be included in a cyclic group. Specific examples of repeating units represented by formula (E) are those described in paragraphs

[0131] to

[0133] of International Publication No. 2018 / 193954.

[0260] (A repeating unit having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups) The resin (A) may have repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups. Examples of repeating units having lactone groups, sultone groups, or carbonate groups in resin (A) include the repeating units described above in <Repeating units having lactone groups, sultone groups, or carbonate groups>. The preferred content is also as described above in <Repeating units having lactone groups, sultone groups, or carbonate groups>.

[0261] The resin (A) may have repeating units having hydroxyl groups or cyano groups. This improves substrate adhesion and developer affinity. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. It is preferable that the repeating units having a hydroxyl group or a cyano group do not have an acid-degradable group. Examples of repeating units having a hydroxyl group or a cyano group are those described in paragraphs

[0081] to

[0084] of Japanese Patent Application Publication No. 2014-098921.

[0262] The resin (A) may have repeating units having alkali-soluble groups. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bissulfonylimide groups, and aliphatic alcohol groups (e.g., hexafluoroisopropanol group) whose α-position is substituted with an electron-withdrawing group, with carboxyl groups being preferred. The inclusion of repeating units having alkali-soluble groups in resin (A) increases the resolution in contact hole applications. Examples of repeating units having alkali-soluble groups include those described in paragraphs

[0085] and

[0086] of Japanese Patent Application Publication No. 2014-098921.

[0263] (A repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposition) Resin (A) may have repeating units that have an alicyclic hydrocarbon structure and do not exhibit acid decomposition. This reduces the elution of low molecular weight components from the resist film into the immersion solution during immersion exposure. Examples of such repeating units include repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0264] (A repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group) Resin (A) may have repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group.

[0265] [ka]

[0266] In formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and lacking both a hydroxyl group and a cyano group. Ra represents a hydrogen atom, an alkyl group, or a -CH2-O-Ra2 group. In the formula, Ra2 represents a hydrogen atom, an alkyl group, or an acyl group. Examples of repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group include those described in paragraphs

[0087] to

[0094] of Japanese Patent Publication No. 2014-098921.

[0267] (Other repeating units) Furthermore, resin (A) may have repeating units other than those described above. For example, resin (A) may have repeating units selected from the group consisting of repeating units having an oxatian ring group, repeating units having an oxazolone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group. Examples of such repeating units are shown below.

[0268] [ka]

[0269] In addition to the repeating structural units described above, resin (A) may have various repeating structural units for the purpose of adjusting dry etching resistance, suitability for standard developers, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

[0270] As for resin (A), (especially when the composition is used as an active photosensitive or radiation-sensitive resin composition for ArF) it is preferable that all of the repeating units are composed of repeating units derived from a compound having an ethylenically unsaturated bond. In particular, it is also preferable that all of the repeating units are composed of (meth)acrylate repeating units. In this case, any of the following can be used: all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are composed of methacrylate repeating units and acrylate repeating units, and it is preferable that the acrylate repeating units make up 50 mol% or less of the total repeating units.

[0271] Resin (A) can be synthesized according to conventional methods (e.g., radical polymerization). According to the GPC method, the weight-average molecular weight of resin (A), expressed as polystyrene equivalent, is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000. The degree of dispersion (molecular weight distribution) of resin (A) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The lower the degree of dispersion, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern and the better the roughness.

[0272] In the composition of the present invention, the content of resin (A) is preferably 40.0 to 99.9% by mass, and more preferably 60.0 to 90.0% by mass, based on the total solid content of the composition. Resin (A) may be used alone or in combination of multiple types.

[0273] <Photoacid Generator> The composition of the present invention may also contain a photoacid generator (B) that does not correspond to compound (I) above. Photoacid generator (B) is a compound that generates the acid necessary for the reaction of the resin in the exposed area. The photoacid generator (B) may be in the form of a low molecular weight compound, or it may be incorporated into a polymer (for example, resin (A) described later). Alternatively, both the form of a low molecular weight compound and the form incorporated into a polymer (for example, resin (A) described later) may be used in combination. When the photoacid generator (B) is in the form of a low molecular weight compound, the molecular weight of the photoacid generator is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less. There is no particular lower limit, but 100 or more is preferred. If the photoacid generator (B) is incorporated into a polymer, it may be incorporated into a resin (A) or into a resin different from resin (A). In the present invention, the photoacid generator (B) is preferably in the form of a low molecular weight compound.

[0274] For example, the photoacid generator (B) is "M + X - Examples include compounds represented by '' (onium salts), and it is preferable that these compounds generate organic acids upon exposure. Examples of the above-mentioned organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methidic acids.

[0275] "M + X - In the compound represented by ", M + This represents an organic cation. The organic cation is not particularly limited. Furthermore, the valency of the organic cation may be 1 or 2 or higher. In particular, the above organic cation is not limited to the above organic cation, but the cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or the cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)") is preferred.

[0276] "M+ X - In the compound represented by ", X - This represents an organic anion. The organic anion is not particularly limited and can be a single-valent or double-valent or higher organic anion. As for the organic anion, anion with a remarkably low ability to undergo nucleophilic reactions is preferred, and non-nucleophilic anions are more preferred.

[0277] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, and camphor sulfonate anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, and aralkyl carboxylic acid anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0278] The aliphatic moiety in aliphatic sulfonic acid anions and aliphatic carboxylic acid anions may be a linear or branched alkyl group or a cycloalkyl group, with linear or branched alkyl groups having 1 to 30 carbon atoms or cycloalkyl groups having 3 to 30 carbon atoms being preferred. The alkyl group described above may be, for example, a fluoroalkyl group (which may have substituents other than a fluorine atom; it may also be a perfluoroalkyl group).

[0279] In aromatic sulfonic acid anions and aromatic carboxylic acid anions, aryl groups having 6 to 14 carbon atoms are preferred, such as phenyl groups, tolyl groups, and naphthyl groups.

[0280] The alkyl, cycloalkyl, and aryl groups listed above may have substituents. Substituents are not particularly limited, but examples include nitro groups, halogen atoms such as fluorine and chlorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), alkyl groups (preferably having 1 to 10 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), alkoxycarbonyl groups (preferably having 2 to 7 carbon atoms), acyl groups (preferably having 2 to 12 carbon atoms), alkoxycarbonyloxy groups (preferably having 2 to 7 carbon atoms), alkylthio groups (preferably having 1 to 15 carbon atoms), alkylsulfonyl groups (preferably having 1 to 15 carbon atoms), alkyliminosulfonyl groups (preferably having 1 to 15 carbon atoms), and aryloxysulfonyl groups (preferably having 6 to 20 carbon atoms).

[0281] In aralkyl carboxylic acid anions, an aralkyl group having 7 to 14 carbon atoms is preferred. Examples of aralkyl groups having 7 to 14 carbon atoms include the benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, and naphthylbutyl group.

[0282] An example of a sulfonylimid anion is the saccharin anion.

[0283] For bis(alkylsulfonyl)imide anions and tris(alkylsulfonyl)methide anions, alkyl groups having 1 to 5 carbon atoms are preferred. Substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, with fluorine atoms or alkyl groups substituted with fluorine atoms being preferred. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion may bond to each other to form a ring structure. This increases the acid strength.

[0284] Other non-nucleophilic anions include, for example, fluorinated phosphorus (e.g., PF6). - ), fluorinated boron (for example, BF4 - ), and fluorinated antimony (e.g., SbF6) - ) are some examples.

[0285] As non-nucleophilic anions, aliphatic sulfonic acid anions in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, aromatic sulfonic acid anions substituted with a fluorine atom or a group having a fluorine atom, bis(alkylsulfonyl)imide anions in which the alkyl group is substituted with a fluorine atom, or tris(alkylsulfonyl)methide anions in which the alkyl group is substituted with a fluorine atom are preferred. Among these, perfluoroaliphatic sulfonic acid anions (preferably with 4 to 8 carbon atoms) or benzenesulfonic acid anions having a fluorine atom are more preferred, and nonafluorobutanesulfonic acid anions, perfluorooctanesulfonic acid anions, pentafluorobenzenesulfonic acid anions, or 3,5-bis(trifluoromethyl)benzenesulfonic acid anions are even more preferred.

[0286] As a non-nucleophilic anion, the anion represented by the following formula (AN1) is also preferred.

[0287] [ka]

[0288] In formula (AN1), R 1 and R 2 Each of these independently represents either a hydrogen atom or a substituent. The substituents are not particularly limited, but groups that are not electron-withdrawing groups are preferred. Examples of groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxy hydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. Furthermore, preferred non-electron-withdrawing groups are, independently, -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR'. R' is a monovalent hydrocarbon group.

[0289] Examples of monovalent hydrocarbon groups represented by R' above include alkyl groups such as methyl, ethyl, propyl, and butyl groups; alkenyl groups such as ethenyl, propenyl, and butenyl groups; monovalent linear or branched hydrocarbon groups such as alkynyl groups such as ethynyl, propynyl, and butynyl groups; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl groups; monovalent alicyclic hydrocarbon groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl groups; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl groups; and monovalent aromatic hydrocarbon groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthrylmethyl groups. Among them, R 1 and R 2 Each of these is independently preferably a hydrocarbon group (cycloalkyl group preferred) or a hydrogen atom.

[0290] L represents a divalent linking group. If there are multiple Ls, each L may be the same or different. Examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably with 1 to 6 carbon atoms), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenylene groups (preferably with 2 to 6 carbon atoms), and divalent linking groups formed by combining multiple thereof. Among these, preferred divalent linking groups are -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO2-, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group-, and more preferred are -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO2-, or -COO-alkylene group-.

[0291] For L, a group represented by the following formula (AN1-1) is preferred. * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (AN1-1)

[0292] In formula (AN1-1), * a R in equation (AN1) 3 This indicates the connection point with [the other element]. * b -C(R 1 )(R 2 )- indicates the connection position with. X and Y each independently represent integers between 0 and 10, preferably between 0 and 3. R 2a and R 2b Each of these independently represents a hydrogen atom or a substituent. R 2a and R 2b If there are multiple instances of each, then there are multiple instances of R 2a and R 2b These may be the same or different. However, if Y is 1 or greater, -C(R) in equation (AN1) 1 )(R 2)- and CR which bind directly 2b R in 2 2b These are atoms other than fluorine atoms. Q is * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or, * A -SO2-* B It represents. However, X+Y in equation (AN1-1) is 1 or greater, and R in equation (AN1-1) 2a and R 2b If all of them are hydrogen atoms, then Q is * A -O-CO-O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or, * A -SO2-* B It represents. * A R in equation (AN1) 3 This indicates the connection position on the side, * B -SO3 in equation (AN1) - This indicates the connection point on the side.

[0293] In formula (AN1), R 3 This represents an organic group. The above organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (e.g., a linear alkyl group), a branched group (e.g., a branched alkyl group such as a t-butyl group), or a cyclic group. The above organic group may or may not have substituents. The above organic group may or may not have heteroatoms (oxygen atom, sulfur atom, and / or nitrogen atom, etc.).

[0294] Among them, R 3 It is preferable that the organic group has a cyclic structure. The cyclic structure may be monocyclic or polycyclic, and may have substituents. It is preferable that the ring in the organic group containing the cyclic structure is directly bonded to L in formula (AN1). The organic group having the above cyclic structure may or may not have heteroatoms (such as oxygen atoms, sulfur atoms, and / or nitrogen atoms). The heteroatoms may substitute for one or more carbon atoms that form the cyclic structure. The organic group having the above-mentioned cyclic structure is preferably a cyclic hydrocarbon group, a lactone ring group, or a sultone ring group. Among these, the organic group having the above-mentioned cyclic structure is preferably a cyclic hydrocarbon group. The hydrocarbon group in the above cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have substituents. The above cycloalkyl group may be monocyclic (e.g., cyclohexyl group) or polycyclic (e.g., adamantyl group), and preferably has 5 to 12 carbon atoms. The lactone group and sultone group described above are preferably groups obtained by removing one hydrogen atom from the ring member atoms constituting the lactone or sultone structure in either of the structures represented by formulas (LC1-1) to (LC1-21) and (SL1-1) to (SL1-3) described above.

[0295] The non-nucleophilic anion may be a benzenesulfonic acid anion, and it is preferable that the benzenesulfonic acid anion is substituted with a branched alkyl group or a cycloalkyl group.

[0296] As a non-nucleophilic anion, the anion represented by the following formula (AN2) is also preferred.

[0297] [ka]

[0298] In equation (AN2), o represents an integer between 1 and 3. p represents an integer between 0 and 10. q represents an integer between 0 and 10.

[0299] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group without a fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Furthermore, perfluoroalkyl groups are preferred as alkyl groups substituted with at least one fluorine atom. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3, and even more preferably both Xf are fluorine atoms.

[0300] R 4 and R 5 Each of these independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. 4 and R 5 If there are multiple instances, R 4 and R 5 These may be the same or different. R 4 and R 5 The alkyl group represented by preferably has 1 to 4 carbon atoms. The alkyl group may have substituents. Hydrogen atoms are preferred for R4 and R5.

[0301] L represents a divalent linking group. The definition of L is the same as L in formula (AN1).

[0302] W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred. Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups. The alicyclic group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.

[0303] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include the phenyl group, naphthyl group, phenanthryl group, and anthryl group. The heterocyclic group may be monocyclic or polycyclic. In particular, a polycyclic heterocyclic group can more effectively suppress acid diffusion. Furthermore, the heterocyclic group may or may not be aromatic. Examples of aromatic heterocyclic rings include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of heterocyclic rings that are not aromatic include tetrahydropyran rings, lactone rings, sultone rings, and decahydroisoquinoline rings. The heterocyclic ring in the heterocyclic group is preferably a furan ring, thiophene ring, pyridine ring, or decahydroisoquinoline ring.

[0304] The above-mentioned cyclic organic group may have substituents. Examples of substituents include alkyl groups (which may be linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, preferably having 3 to 20 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamide groups, and sulfonic acid ester groups. The carbon atoms constituting the cyclic organic group (carbon atoms contributing to ring formation) may be carbonyl carbons.

[0305] The anion represented by formula (AN2) is SO3. - -CF2-CH2-OCO-(L) q’ -W, SO3 - -CF2-CHF-CH2-OCO-(L) q’ -W, SO3 - -CF2-COO-(L) q’ -W, SO3 - -CF2-CF2-CH2-CH2-(L) q -W, or SO3 - -CF2-CH(CF3)-OCO-(L) q’ -W is preferred. Here, L, q, and W are the same as in equation (AN2). q' represents an integer from 0 to 10.

[0306] As a non-nucleophilic anion, an aromatic sulfonic acid anion represented by the following formula (AN3) is also preferred.

[0307] [ka]

[0308] In formula (AN3), Ar represents an aryl group (such as a phenyl group), and may further have substituents other than a sulfonic acid anion and a -(DB) group. Examples of further substituents include a fluorine atom and a hydroxyl group. n represents a non-negative integer. n is preferably between 1 and 4, more preferably between 2 and 3, and even more preferably 3.

[0309] D represents a single bond or a divalent linking group. Examples of divalent linking groups include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonic acid ester groups, ester groups, and groups consisting of two or more combinations of these.

[0310] B represents a hydrocarbon group. For B, an aliphatic hydrocarbon group is preferred, and an isopropyl group, a cyclohexyl group, or an aryl group which may have further substituents (such as a tricyclohexylphenyl group) is more preferred.

[0311] As a non-nucleophilic anion, disulfonamide anions are also preferred. Disulfonamide anions are, for example, N - (SO2-R q This is an anion represented by 2. Here, R q R represents an alkyl group which may have substituents, fluoroalkyl groups are preferred, and perfluoroalkyl groups are more preferred. q They may be joined to each other to form a ring. Two R q The group formed by the bonding of these atoms is preferably an alkylene group, which may have substituents, preferably a fluoroalkylene group, and more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0312] Furthermore, non-nucleophilic anions include those represented by the following formulas (d1-1) to (d1-4).

[0313] [ka]

[0314] [ka]

[0315] In formula (d1-1), R 51 represents a hydrocarbon group (for example, an aryl group such as a phenyl group) which may have substituents (for example, a hydroxyl group).

[0316] In formula (d1-2), Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms, which may have substituents (however, carbon atoms adjacent to S are not substituted with fluorine atoms). Z 2c The hydrocarbon group in the above may be linear, branched, or have a cyclic structure. Furthermore, the carbon atoms in the hydrocarbon group (preferably, the ring member carbon atoms when the hydrocarbon group has a cyclic structure) may be carbonyl carbons (-CO-). Examples of the hydrocarbon group include a group having a norbornyl group, which may have substituents. The carbon atoms forming the norbornyl group may also be carbonyl carbons. Also, in equation (d1-2) "Z 2c -SO3 - It is preferable that the anion represented by the above formulas (AN1) to (AN3) is different from the anion. For example, Z 2c It is preferable that it is not an aryl group. Also, for example, Z 2c -SO3 - For the α and β positions, atoms other than carbon atoms having a fluorine atom as a substituent are preferred. For example, Z 2c is, -SO3 - Preferably, the atom at the α position and / or the atom at the β position are ring member atoms in the cyclic group.

[0317] In formula (d1-3), R 52 represents an organic group (preferably a hydrocarbon group having a fluorine atom), Y 3 Rf represents a linear, branched, or cyclic alkylene, arylene, or carbonyl group, while Rf represents a hydrocarbon group.

[0318] In formula (d1-4), R 53 and R 54 Each of these independently represents an organic group (preferably a hydrocarbon group having a fluorine atom).53 and R 54 They may be joined to each other to form a ring.

[0319] Organic anions may be used individually or in combination of two or more.

[0320] The photoacid generator is preferably at least one selected from the group consisting of compounds (1) to (2).

[0321] (Compound (1)) Compound (1) is a compound having one or more of the following structural sites X and one or more of the following structural sites Y, which generates an acid containing a first acidic site derived from the following structural site X and a second acidic site derived from the following structural site Y upon irradiation with active light or radiation. Structural part X: Anion part A1 - and cation site M1 + It consists of the above, and upon irradiation with active light or radiation, it forms a structural site that forms a first acidic site represented by HA1. Structural site Y: Anionic site A2 - and cation site M2 + It consists of the above, and upon irradiation with active light or radiation, a structural site which forms a second acidic site represented by HA2. Furthermore, the above compound (1) satisfies the following condition I.

[0322] Condition I: In the above compound (1), the above cation site M1 in the above structural site X + and the cation portion M2 in the structural portion Y + to H + The compound PI obtained by replacing the above structural site X is the above cation site M1 + to H + The acid dissociation constant a1 derived from the acidic site represented by HA1, which is replaced by the above-mentioned cation site M2 in the above-mentioned structural site Y + to H + It has an acid dissociation constant a2 derived from the acidic site represented by HA2, which is replaced by the above acid dissociation constant a1, and the above acid dissociation constant a2 is greater than the above acid dissociation constant a1.

[0323] Condition I will be explained in more detail below. If compound (1) is a compound that generates an acid having, for example, one first acidic site derived from structural site X and one second acidic site derived from structural site Y, then compound PI falls under the category of "a compound having HA1 and HA2". To explain more specifically, when the acid dissociation constants a1 and a2 of compound PI are determined, if compound PI is "A1 - The pKa of the compound having HA2 is the acid dissociation constant a1, and the above "A1 - "A compound having HA2" is "A1 - and A2 - The pKa of the compound having the above characteristics is the acid dissociation constant a2.

[0324] Furthermore, if compound (1) is a compound that generates an acid having, for example, two first acidic sites derived from structural site X and one second acidic site derived from structural site Y, then compound PI falls under the category of "a compound having two HA1 and one HA2". When the acid dissociation constant of such compound PI is determined, compound PI is "one A1 - The acid dissociation constant when a compound having one HA1 and one HA2 is formed, and the acid dissociation constant when a compound having one A1 - "A compound having one HA1 and one HA2" is "two A1 - The acid dissociation constant when forming a compound having "and one HA2" corresponds to the above-mentioned acid dissociation constant a1. Also, "two A1 - A compound having one HA2 is a compound having two A1 - and A2 - The acid dissociation constant when a compound has the above-mentioned cation site M1 corresponds to the acid dissociation constant a2. In other words, in the case of such a compound PI, the above-mentioned cation site M1 in the above-mentioned structural site X + to H +When there are a plurality of acid dissociation constants derived from the acidic site represented by HA1 which is replaced, the value of the acid dissociation constant a2 is larger than the largest value among the plurality of acid dissociation constants a1. In addition, when the compound PI is "one A1 - and a compound having one HA1 and one HA2", the acid dissociation constant is aa, and "one A1 - and a compound having one HA1 and one HA2" becomes "two A1 - and when the acid dissociation constant when having one HA2 is ab, the relationship between aa and ab satisfies aa < ab.

[0325] The acid dissociation constant a1 and the acid dissociation constant a2 are determined by the measurement method of the acid dissociation constant described above. The above compound PI corresponds to the acid generated when the compound (1) is irradiated with actinic rays or radiation. When the compound (1) has two or more structural sites X, the structural sites X may be the same or different from each other. Also, two or more of the above A1 - , and two or more of the above M1 + may be the same or different from each other. Also, in the compound (1), the above A1 - and the above A2 - , and the above M1 + and the above M2 + may be the same or different from each other, but the above A1 - and the above A2 - are preferably different from each other.

[0326] In the above compound PI, the difference (absolute value) between the acid dissociation constant a1 (when there are a plurality of acid dissociation constants a1, the maximum value thereof) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and still more preferably 1.0 or more. The upper limit value of the difference (absolute value) between the acid dissociation constant a1 (when there are a plurality of acid dissociation constants a1, the maximum value thereof) and the acid dissociation constant a2 is not particularly limited, but for example, it is 16 or less.

[0327] In the above compound PI, the acid dissociation constant a2 is preferably 20 or less, and more preferably 15 or less. The lower limit of the acid dissociation constant a2 is preferably -4.0 or higher.

[0328] Furthermore, in the above compound PI, the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less. The lower limit of the acid dissociation constant a1 is preferably -20.0 or higher.

[0329] Anion part A1 - and anion part A2 - This refers to a structural site containing a negatively charged atom or group of atoms, and examples include structural sites selected from the group consisting of formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) shown below. Anion part A1 - Preferably, the acidic site can form an acidic site with a small acid dissociation constant, and among these, it is more preferably one of formulas (AA-1) to (AA-3), and even more preferably one of formulas (AA-1) and (AA-3). Also, anion part A2 - For example, Anion part A1 - It is preferable that the material can form an acidic site with a larger acid dissociation constant than the other material, more preferably one of formulas (BB-1) to (BB-6), and even more preferably one of formulas (BB-1) and (BB-4). In the following equations (AA-1) to (AA-3) and (BB-1) to (BB-6), * indicates the bond position. In formula (AA-2), R A R represents a monovalent organic group. A The monovalent organic group represented by is not particularly limited, but examples include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0330] [ka] JPEG0007853983000074.jpg20130

[0331] Also, cationic moiety M1 + and cationic moiety M2 + are structural moieties containing an atom or atomic group with a positive charge, and examples thereof include monovalent organic cations. The organic cation includes, for example, the M + represented organic cation.

[0332] The specific structure of the compound (1) is not particularly limited, and examples thereof include compounds represented by the following formulas (Ia-1) to (Ia-5).

[0333] -Compound represented by formula (Ia-1)- Hereinafter, first, the compound represented by formula (Ia-1) will be described.

[0334] M 11 + A 11 - -L1-A 12 - M 12 + (Ia-1)

[0335] The compound represented by formula (Ia-1) generates an acid represented by HA 11 -L1-A 12 H upon irradiation with actinic rays or radiation.

[0336] In formula (Ia-1), M 11 + and M 12 + each independently represent an organic cation. A 11 - and A 12 - each independently represent a monovalent anionic functional group. L1 represents a divalent linking group. M 11 + and M 12 + may be the same or different from each other. A 11- and A 12 - These elements may be the same or different, but it is preferable that they are different from each other. However, in the above formula (Ia-1), M 11 + and M 12 + The cation represented by H + The compound PIa(HA) is formed by replacing it with PIa(HA) 11 -L1-A 12 In H), A 12 The acid dissociation constant a2, which originates from the acidic site represented by H, is HA 11 It is greater than the acid dissociation constant a1 derived from the acidic site represented by (Ia-1). The preferred values ​​for the acid dissociation constants a1 and a2 are as described above. Furthermore, the acid generated from compound PIa and the compound represented by formula (Ia-1) upon irradiation with active light or radiation is the same. Also, M 11 + M 12 + , A 11 - , A 12 - , and at least one of L1 may have an acid-degradable group as a substituent.

[0337] In formula (Ia-1), M 11 + and M 12 + The organic cations represented by the above M are as follows: + Examples of organic cations represented by the following are given.

[0338] A 11 - The monovalent anionic functional group represented by is the anionic moiety A1 mentioned above. - This refers to a monovalent group including A. 12 - The monovalent anionic functional group represented by is the anionic moiety A2 mentioned above. - This refers to a monovalent group that includes [the specified element]. A 11 - and A12 - The monovalent anionic functional group represented by is preferably a monovalent anionic functional group containing any of the anionic moieties of formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) described above, and more preferably a monovalent anionic functional group selected from the group consisting of formulas (AX-1) to (AX-3) and formulas (BX-1) to (BX-7). 11 - Among the monovalent anionic functional groups represented by (AX-1) to (AX-3), it is preferable that they be monovalent anionic functional groups represented by any of the formulas (AX-1) to (AX-3). 12 - Among the monovalent anionic functional groups represented by (BX-1) to (BX-7), a monovalent anionic functional group represented by any of the formulas (BX-1) to (BX-6) is preferred, and a monovalent anionic functional group represented by any of the formulas (BX-1) to (BX-6) is more preferred.

[0339] [ka]

[0340] In formulas (AX-1) to (AX-3), R A1 and R A2 Each of these independently represents a monovalent organic group. * represents a bond position. R A1 The monovalent organic group represented by is not particularly limited, but examples include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0341] R A2 The monovalent organic group represented by is preferably a linear, branched, or cyclic alkyl group, or an aryl group. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6. The alkyl group described above may have substituents. Preferably, the substituents are fluorine atoms or cyano groups, and more preferably fluorine atoms. If the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.

[0342] The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The above aryl group may have substituents. Preferred substituents are fluorine atoms, iodine atoms, perfluoroalkyl groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred), or cyano groups, with fluorine atoms, iodine atoms, or perfluoroalkyl groups being more preferred.

[0343] In equations (BX-1) to (BX-4) and (BX-6), R B represents a monovalent organic group. * represents a bond position. R B The monovalent organic group represented by is preferably a linear, branched, or cyclic alkyl group, or an aryl group. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6. The alkyl group described above may have substituents. While the substituents are not particularly limited, fluorine atoms or cyano groups are preferred, with fluorine atoms being more preferred. If the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group. In addition, the carbon atoms that become the bonding positions in the alkyl group (for example, in the cases of formulas (BX-1) and (BX-4), the carbon atoms directly bonded to the -CO- explicitly stated in the formula of the alkyl group; in the cases of formulas (BX-2) and (BX-3), the carbon atoms directly bonded to the -SO2- explicitly stated in the formula of the alkyl group; and in the case of formula (BX-6), the carbon atoms explicitly stated in the formula of the alkyl group) are the N - This refers to the carbon atom that is directly bonded to it. If the atom has substituents, it is also preferable that the substituents are other than a fluorine atom or a cyano group. Furthermore, the alkyl group may have carbon atoms substituted with carbonyl carbons.

[0344] The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The above aryl group may have substituents. Preferred substituents include fluorine atoms, iodine atoms, perfluoroalkyl groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred), cyano groups, alkyl groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred), alkoxy groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred), and fluorine atoms, iodine atoms, perfluoroalkyl groups, alkyl groups, alkoxy groups, or alkoxycarbonyl groups are more preferred.

[0345] In formula (Ia-1), the divalent linking group represented by L1 is not particularly limited and may be -CO-, -NR-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene group (preferably having 1 to 6 carbon atoms; may be linear or branched), cycloalkylene group (preferably having 3 to 15 carbon atoms), alkenylene group (preferably having 2 to 6 carbon atoms), or a divalent aliphatic heterocyclic group (having at least one N, O, S, or Se atom in the ring structure). Examples include 5-10 membered rings, more preferably 5-7 membered rings, and even more preferably 5-6 membered rings, divalent aromatic heterocyclic groups (5-10 membered rings having at least one N, O, S, or Se atom in the ring structure, more preferably 5-7 membered rings, and even more preferably 5-6 membered rings), divalent aromatic hydrocarbon ring groups (6-10 membered rings, and even more preferably 6 membered rings), and divalent linking groups formed by combining several of these. The above R can be a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but for example, alkyl groups (preferably having 1 to 6 carbon atoms) are preferred. Furthermore, the alkylene group, cycloalkylene group, alkenylene group, divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group, and divalent aromatic hydrocarbon ring group may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0346] In particular, the divalent linking group represented by L1 is preferably the divalent linking group represented by formula (L1).

[0347] [ka]

[0348] In formula (L1), L 111 This represents a single bond or a divalent linking group. L 111 The divalent linking group represented by is not particularly limited and includes, for example, -CO-, -NH-, -O-, -SO-, -SO2-, optionally substituted alkylene groups (preferably having 1 to 6 carbon atoms, and may be linear or branched), optionally substituted cycloalkylene groups (preferably having 3 to 15 carbon atoms), optionally substituted aryl groups (preferably having 6 to 10 carbon atoms), and divalent linking groups formed by combining several of these. The substituent is not particularly limited and includes, for example, halogen atoms. p represents an integer between 0 and 3, preferably between 1 and 3. v represents an integer, either 0 or 1. Each Xf1 independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Furthermore, perfluoroalkyl groups are preferred as alkyl groups substituted with at least one fluorine atom. Each Xf2 independently represents a hydrogen atom, an alkyl group which may have a fluorine atom as a substituent, or a fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Among these, Xf2 preferably represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and more preferably a fluorine atom or a perfluoroalkyl group. Among them, Xf1 and Xf2 are each independently preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3. In particular, it is further preferred that both Xf1 and Xf2 are fluorine atoms. * represents the bonding position. L in formula (Ia-1) 11 When it represents a divalent linking group represented by formula (L1), L in formula (L1) 111 The bond (*) on the side is preferably bonded to A in formula (Ia-1) 12 - and.

[0349] - Compounds represented by formula (Ia-2) to (Ia-4) - Next, the compounds represented by formula (Ia-2) to (Ia-4) will be described.

[0350]

Chemical formula

[0351] In formula (Ia-2), A 21a - and A 21b - each independently represents a monovalent anionic functional group. Here, the monovalent anionic functional group represented by A 21a - and A 21b - is intended to be a monovalent group containing the above-mentioned anionic moiety A1 - . The monovalent anionic functional group represented by A 21a - and A 21b - is not particularly limited, and examples thereof include monovalent anionic functional groups selected from the group consisting of the above-mentioned formulas (AX-1) to (AX-3). A 22 - represents a divalent anionic functional group. Here, the divalent anionic functional group represented by A 22 - is the above-mentioned anionic moiety A2 -This refers to a divalent group containing A. 22 - Examples of divalent anionic functional groups represented by the formulas (BX-8) to (BX-11) shown below include the divalent anionic functional groups represented by the formulas (BX-8) to (BX-11).

[0352] [ka]

[0353] M 21a + M 21b + , and M 22 + Each of these independently represents an organic cation. 21a + M 21b + , and M 22 + The organic cation represented by the above M is 11 + This is synonymous with the same thing, and the preferred embodiment is also the same. L 21 and L 22 Each of these independently represents a divalent organic group.

[0354] Furthermore, in the above equation (Ia-2), M 21a + M 21b + , and M 22 + The organic cation represented by H + In compound PIa-2, which is obtained by substituting A, 22 The acid dissociation constant a2, which originates from the acidic site represented by H, is A 21a Acid dissociation constants a1-1 and A derived from H 21b It is greater than the acid dissociation constant a1-2, which originates from the acidic site represented by H. Note that the acid dissociation constants a1-1 and a1-2 correspond to the acid dissociation constant a1 mentioned above. Note A 21a - and A 21b - They may be the same or different from each other. Also, M21a + M 21b + , and M 22 + They may be the same or different from one another. Also, M 21a + M 21b + M 22 + , A 21a - , A 21b - , L 21 , and L 22 At least one of these may have an acid-degradable group as a substituent.

[0355] In equation (Ia-3), A 31a - and A 32 - Each of these independently represents a monovalent anionic functional group. 31a - The definition of a monovalent anionic functional group represented by is A in formula (Ia-2) above. 21a - and A 21b - This is synonymous with the same thing, and the preferred embodiment is also the same. A 32 - The monovalent anionic functional group represented by is the anionic moiety A2 described above. - This refers to a monovalent group containing A. 32 - The monovalent anionic functional group represented by is not particularly limited, but examples include monovalent anionic functional groups selected from the group consisting of the above formulas (BX-1) to (BX-7). A 31b - represents a divalent anionic functional group. Here, A 31b - The divalent anionic functional group represented by is the anionic moiety A1 mentioned above. - This refers to a divalent group containing A. 31b -Examples of divalent anionic functional groups represented by the formula (AX-4) shown below include the divalent anionic functional group represented by the formula (AX-4).

[0356] [ka]

[0357] M 31a + M 31b + , and M 32 + Each of these independently represents a monovalent organic cation. 31a + M 31b + , and M 32 + The organic cation represented by the above M is 11 + This is synonymous with the same thing, and the preferred embodiment is also the same. L 31 and L 32 Each of these independently represents a divalent organic group.

[0358] Furthermore, in the above equation (Ia-3), M 31a + M 31b + , and M 32 + The organic cation represented by H + In compound PIa-3, which is obtained by substituting A, 32 The acid dissociation constant a2, which originates from the acidic site represented by H, is A 31a Acid dissociation constants a1-3 and A, derived from the acidic site represented by H. 31b It is larger than the acid dissociation constant a1-4, which originates from the acidic site represented by H. Note that the acid dissociation constants a1-3 and a1-4 correspond to the acid dissociation constant a1 mentioned above. Note A 31a - and A 32 - They may be the same or different from each other. Also, M 31a + M31b + , and M 32 + They may be the same or different from one another. Also, M 31a + M 31b + M 32 + , A 31a - , A 32 - , L 31 , and L 32 At least one of these may have an acid-degradable group as a substituent.

[0359] In equation (Ia-4), A 41a - , A 41b - , and A 42 - Each of these independently represents a monovalent anionic functional group. 41a - and A 41b - The definition of a monovalent anionic functional group represented by is A in formula (Ia-2) above. 21a - and A 21b - It is synonymous with A. 42 - The definition of a monovalent anionic functional group represented by is A in formula (Ia-3) above. 32 - This is synonymous with the same thing, and the preferred embodiment is also the same. M 41a + M 41b + , and M 42 + Each of these independently represents an organic cation. 41a + M 41b + , and M 42 + The organic cation represented by the above M is 11 + This is synonymous with the same thing, and the preferred embodiment is also the same. L41 This represents a trivalent organic group.

[0360] Furthermore, in the above equation (Ia-4), M 41a + M 41b + , and M 42 + The organic cation represented by H + In compound PIa-4, which is obtained by substituting A, 42 The acid dissociation constant a2, which originates from the acidic site represented by H, is A 41a Acid dissociation constants a1-5 and A, derived from the acidic site represented by H. 41b It is larger than the acid dissociation constant a1-6, which originates from the acidic site represented by H. Note that the acid dissociation constants a1-5 and a1-6 correspond to the acid dissociation constant a1 mentioned above. Note A 41a - , A 41b - , and A 42 - They may be the same or different from each other. Also, M 41a + M 41b + , and M 42 + They may be the same or different from one another. Also, M 41a + M 41b + M 42 + , A 41a - , A 41b - , A 42 - , and L 41 At least one of these may have an acid-degradable group as a substituent.

[0361] L in equation (Ia-2) 21 and L 22 , and also L in equation (Ia-3) 31 and L 32The divalent organic group represented by is not particularly limited and includes, for example, -CO-, -NR-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms; may be linear or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), divalent aliphatic heterocyclic groups (preferably 5 to 10-membered rings having at least one N, O, S, or Se atom in the ring structure, more preferably 5 to 7-membered rings, and even more preferably 5 to 6-membered rings), divalent aromatic heterocyclic groups (preferably 5 to 10-membered rings having at least one N, O, S, or Se atom in the ring structure, more preferably 5 to 7-membered rings, and even more preferably 5 to 6-membered rings), divalent aromatic hydrocarbon ring groups (preferably 6 to 10-membered rings, and even more preferably 6-membered rings), and divalent organic groups formed by combining several of these. The above R can be a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferred. Furthermore, the alkylene group, cycloalkylene group, alkenylene group, divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group, and divalent aromatic hydrocarbon ring group may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0362] L in equation (Ia-2) 21 and L 22 , and also L in equation (Ia-3) 31 and L 32 The divalent organic group represented by is preferably, for example, the divalent organic group represented by the following formula (L2).

[0363] [ka]

[0364] In equation (L2), q represents an integer between 1 and 3. * indicates the joining position. Each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Furthermore, perfluoroalkyl groups are preferred as alkyl groups substituted with at least one fluorine atom. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF3. In particular, it is even more preferable that both Xf are fluorine atoms.

[0365] L A This represents a single bond or a divalent linking group. L A The divalent linking group represented by is not particularly limited and includes, for example, -CO-, -O-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms; may be linear or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), divalent aromatic hydrocarbon ring groups (preferably 6 to 10 membered rings, more preferably 6 membered rings), and divalent linking groups formed by combining several of these. Furthermore, the alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0366] Examples of divalent organic groups represented by formula (L2) include *-CF2-*, *-CF2-CF2-*, *-CF2-CF2-CF2-*, *-Ph-O-SO2-CF2-*, *-Ph-O-SO2-CF2-CF2-*, *-Ph-O-SO2-CF2-CF2-CF2-*, and *-Ph-OCO-CF2-*. Herein, Ph is a phenylene group which may have substituents, and is preferably a 1,4-phenylene group. The substituents are not particularly limited, but alkyl groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are preferred), alkoxy groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are preferred), or alkoxycarbonyl groups (for example, those having 2 to 10 carbon atoms are preferred, and those having 2 to 6 carbon atoms are preferred). L in equation (Ia-2) 21 and L 22 When represents a divalent organic group represented by formula (L2), the L in formula (L2) A The side joint (*) is A in equation (Ia-2). 21a - and A 21b - It is preferable to combine it with this. Also, L in equation (Ia-3) 31 and L 32 When represents a divalent organic group represented by formula (L2), the L in formula (L2) A The side joint (*) is A in equation (Ia-3). 31a - and A 32 - It is preferable to combine it with this.

[0367] - Compound represented by formula (Ia-5) - Next, let's explain equation (Ia-5).

[0368] [ka]

[0369] In equation (Ia-5), A 51a - , A 51b - , and A 51c - Each of these independently represents a monovalent anionic functional group. Here, A 51a - , A 51b - , and A 51c - The monovalent anionic functional group represented by is the anionic moiety A1 mentioned above. - This refers to a monovalent group containing A. 51a - , A 51b - , and A 51c -The monovalent anionic functional group represented by is not particularly limited, but examples include monovalent anionic functional groups selected from the group consisting of the above formulas (AX-1) to (AX-3). A 52a - and A 52b - represents a divalent anionic functional group. Here, A 52a - and A 52b - The divalent anionic functional group represented by is the anionic moiety A2 mentioned above. - This refers to a divalent group containing A. 22 - Examples of divalent anionic functional groups represented by the above formulas (BX-8) to (BX-11) include divalent anionic functional groups selected from the group.

[0370] M 51a + M 51b + M 51c + M 52a + , and M 52b + Each of these independently represents an organic cation. 51a + M 51b + M 51c + M 52a + , and M 52b + The organic cation represented by the above M is 11 + This is synonymous with the same thing, and the preferred embodiment is also the same. L 51 and L 53 Each of these independently represents a divalent organic group. 51 and L 53 As a divalent organic group represented by the above formula (Ia-2), L 21 and L 22 This is synonymous with the same thing, and the preferred embodiment is also the same. L 52 L represents a trivalent organic group.52 As a trivalent organic group represented by the above formula (Ia-4), L 41 This is synonymous with the same thing, and the preferred embodiment is also the same.

[0371] Furthermore, in the above equation (Ia-5), M 51a + M 51b + M 51c + M 52a + , and M 52b + The organic cation represented by H + In compound PIa-5, which is obtained by substituting A, 52a Acid dissociation constants a2-1 and A, which originate from the acidic site represented by H. 52b The acid dissociation constant a2-2, which originates from the acidic site represented by H, is A 51a Acid dissociation constants a1-1 and A derived from H. 51b Acid dissociation constants a1-2 and A originate from the acidic site represented by H. 51c This is greater than the acid dissociation constant a1-3 derived from the acidic site represented by H. Note that acid dissociation constants a1-1 to a1-3 correspond to the acid dissociation constant a1 mentioned above, and acid dissociation constants a2-1 and a2-2 correspond to the acid dissociation constant a2 mentioned above. Note A 51a - , A 51b - , and A 51c - They may be the same or different from each other. Also, A 52a - and A 52b - They may be the same or different from each other. Also, M 51a + M 51b + M 51c + M 52a + , and M 52b + They may be the same or different from one another. Also, M 51b + M51c + M 52a + M 52b + , A 51a - , A 51b - , A 51c - , L 51 , L 52 , and L 53 At least one of these may have an acid-degradable group as a substituent.

[0372] (Compound (2)) Compound (2) is a compound having two or more of the above-mentioned structural sites X and one or more of the following structural sites Z, and is a compound that generates an acid, including a compound that generates an acid containing two or more of the above-mentioned first acidic sites derived from the above-mentioned structural sites X and the above-mentioned structural sites Z, upon irradiation with active light or radiation. Structural site Z: A nonionic site capable of neutralizing acids.

[0373] Definition of structural site X in compound (2), and A1 - and M1 + The definition is the definition of structural site X in compound (1) described above, and A1 - and M1 + This is synonymous with the definition of [the specified term], and the preferred embodiment is also the same.

[0374] In the above compound (2), the above cation moiety M1 in the above structural moiety X + to H + In compound PII obtained by replacing with the above structural site X, the above cation site M1 + to H + The preferred range for the acid dissociation constant a1 derived from the acidic moiety represented by HA1, which is obtained by replacing it with the above compound PI, is the same as the acid dissociation constant a1 in the above compound PI. Furthermore, if compound (2) is, for example, a compound that generates an acid having two of the first acidic sites derived from the above structural site X and the above structural site Z, then compound PII corresponds to "a compound having two HA1s". When the acid dissociation constant of this compound PII is determined, compound PII corresponds to "one A1 - The acid dissociation constant when a compound having "one HA1" is formed, and "one A1 - A compound having one HA1 is a compound having two A1 - The acid dissociation constant when a compound becomes "a compound having " corresponds to the acid dissociation constant a1.

[0375] The acid dissociation constant a1 is determined by the acid dissociation constant measurement method described above. The above compound PII refers to the acid generated when compound (2) is irradiated with active light or radiation. Note that the two or more structural parts X described above may be the same or different. Also, two or more of the above A1 - , and two or more of the above M1 + These may be the same or different.

[0376] The nonionic site in structural site Z that can neutralize the acid is not particularly limited, but is preferably, for example, a site that can electrostatically interact with a proton or a site that contains an electron-containing functional group. Examples of functional groups that can electrostatically interact with protons, or that have electrons, include functional groups having a macrocyclic structure such as cyclic polyethers, or functional groups having a nitrogen atom with a lone pair of electrons that does not contribute to π-conjugation. A nitrogen atom having a lone pair of electrons that does not contribute to π-conjugation is, for example, a nitrogen atom having the substructure shown in the following formula.

[0377] [ka]

[0378] Examples of substructures of functional groups having a group or electron that can electrostatically interact with a proton include crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures, among which primary to tertiary amine structures are preferred.

[0379] Compound (2) is not particularly limited, but examples include compounds represented by the following formulas (IIa-1) and (IIa-2).

[0380] [ka]

[0381] In the above equation (IIa-1), A 61a - and A 61b - These are A in equation (Ia-1) mentioned above. 11 - It is synonymous with the same as the preferred embodiment. Also, M 61a + and M 61b + These are M in equation (Ia-1) described above. 11 + This is synonymous with the same thing, and the preferred embodiment is also the same. In the above equation (IIa-1), L 61 and L 62 These terms are equivalent to L1 in the above-mentioned formula (Ia-1), and the preferred embodiments are the same.

[0382] In formula (IIa-1), R 2X R represents a monovalent organic group. 2X The monovalent organic group represented by is not particularly limited, and examples include alkyl groups (preferably having 1 to 10 carbon atoms; may be linear or branched), cycloalkyl groups (preferably having 3 to 15 carbon atoms), or alkenyl groups (preferably having 2 to 6 carbon atoms), in which -CH2- may be substituted with one or more selected from the group consisting of -CO-, -NH-, -O-, -S-, -SO-, and -SO2-. Furthermore, the alkylene group, the cycloalkylene group, and the alkenylene group may have substituents. The substituents are not particularly limited, but examples include halogen atoms (preferably fluorine atoms).

[0383] Furthermore, in the above equation (IIa-1), M 61a + and M 61b + The organic cation represented by H + In compound PIIa-1, which is obtained by substituting A, 61a Acid dissociation constants a1-7 and A, derived from the acidic site represented by H. 61b The acid dissociation constants a1-8, derived from the acidic site represented by H, correspond to the acid dissociation constant a1 mentioned above. Furthermore, in the above compound (IIa-1), the above cation site M in the above structural site X. 61a + and M 61b + to H + Compound PIIa-1, which is obtained by replacing HA, 61a -L 61 -N(R 2X )-L 62 -A 61b H is the corresponding element. Furthermore, compound PIIa-1 and the acid generated from the compound represented by formula (IIa-1) upon irradiation with active light or radiation are the same. Also, M 61a + M 61b + , A 61a - , A 61b - , L 61 , L 62 , and R 2X At least one of these may have an acid-degradable group as a substituent.

[0384] In the above equation (IIa-2), A 71a - , A 71b - , and A 71c - These are A in equation (Ia-1) mentioned above.11 - It is synonymous with the same as the preferred embodiment. Also, M 71a + M 71b + , and M 71c + These are M in equation (Ia-1) described above. 11 + This is synonymous with the same thing, and the preferred embodiment is also the same. In the above equation (IIa-2), L 71 , L 72 , and L 73 These terms are equivalent to L1 in the above-mentioned formula (Ia-1), and the preferred embodiments are the same.

[0385] Furthermore, in the above equation (IIa-2), M 71a + M 71b + , and M 71c + The organic cation represented by H + In compound PIIa-2, which is obtained by substituting A, 71a Acid dissociation constants a1-9 and A, derived from the acidic site represented by H. 71b Acid dissociation constants a1-10 and A originate from the acidic site represented by H. 71c The acid dissociation constants a1-11, derived from the acidic site represented by H, correspond to the acid dissociation constant a1 mentioned above. Furthermore, in the above compound (IIa-1), the above cation site M in the above structural site X. 71a + M 71b + , and M 71c + to H + Compound PIIa-2, which is obtained by replacing HA, 71a -L 71 -N(L 73 -A 71c H)-L 72 -A 71b H is the corresponding element. Furthermore, compound PIIa-2 and the acid generated from the compound represented by formula (IIa-2) upon irradiation with active light or radiation are the same. Also, M 71a+ M 71b + M 71c + , A 71a - , A 71b - , A 71c - , L 71 , L 72 , and L 73 At least one of these may have an acid-degradable group as a substituent.

[0386] Examples of non-cationic sites that compounds (1) and (2) may possess are given below.

[0387] [ka]

[0388] [ka]

[0389] The following are specific examples of photoacid generators, but are not limited to these.

[0390] [ka]

[0391] [ka]

[0392] [ka]

[0393] When the composition of the present invention contains a photoacid generator (B), its content is not particularly limited, but it is preferably 0.5% by mass or more, and more preferably 1.0% by mass or more, relative to the total solid content of the composition, in that the cross-sectional shape of the formed pattern becomes more rectangular. Furthermore, the above content is preferably 50.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less, relative to the total solid content of the composition. The photoacid generator (B) may be used alone or in combination of two or more types.

[0394] <Acid diffusion control agent> The composition of the present invention may also contain an acid diffusion control agent (C) that does not correspond to compound (I) above. The acid diffusion control agent traps the acid generated from photoacid generators during exposure and acts as a quencher to suppress the reaction of acid-degradable resins in unexposed areas due to excess generated acid. The type of acid diffusion control agent is not particularly limited and includes, for example, basic compounds (CA), low molecular weight compounds (CB) having a nitrogen atom and a group that is eliminated by the action of an acid, and compounds (CC) whose acid diffusion control ability is reduced or lost by irradiation with active light or radiation. Examples of compounds (CC) include onium salt compounds (CD) that are relatively weak acids with respect to the photoacid generator, and basic compounds (CE) whose basicity decreases or disappears upon irradiation with active light or radiation. Furthermore, for example, specific examples of basic compounds (CA) include those described in paragraphs

[0132] to

[0136] of International Publication No. 2020 / 066824; specific examples of basic compounds (CE) whose basicity is reduced or lost by irradiation with active light or radiation include those described in paragraphs

[0137] to

[0155] of International Publication No. 2020 / 066824; specific examples of low molecular weight compounds (CB) having a nitrogen atom and a group that is eliminated by the action of an acid include those described in paragraphs

[0156] to

[0163] of International Publication No. 2020 / 066824; and specific examples of onium salt compounds (CE) having a nitrogen atom in the cation portion include those described in paragraph

[0164] of International Publication No. 2020 / 066824. Furthermore, specific examples of onium salt compounds (CDs) that are relatively weak acids with respect to photoacid generators include those described in paragraphs

[0305] to

[0314] of International Publication No. 2020 / 158337.

[0395] In addition to the above, known compounds disclosed in paragraphs

[0627] to

[0664] of U.S. Patent Application Publication 2016 / 0070167A1, paragraphs

[0095] to

[0187] of U.S. Patent Application Publication 2015 / 0004544A1, paragraphs

[0403] to

[0423] of U.S. Patent Application Publication 2016 / 0237190A1, and paragraphs

[0259] to

[0328] of U.S. Patent Application Publication 2016 / 0274458A1 can be suitably used as acid diffusion control agents.

[0396] If the composition of the present invention contains an acid diffusion control agent, the content of the acid diffusion control agent (total if there are multiple types) is preferably 0.1 to 15.0% by mass, and more preferably 1.0 to 15.0% by mass, based on the total solid content of the composition. In the composition of the present invention, one acid diffusion control agent may be used alone, or two or more may be used in combination.

[0397] <Hydrophobic resin> The composition of the present invention may further contain a hydrophobic resin (D) different from resin (A). Hydrophobic resins are preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, they do not necessarily need to have hydrophilic groups within their molecules and do not need to contribute to the uniform mixing of polar and nonpolar substances. The effects of adding hydrophobic resins include controlling the static and dynamic contact angles of the resist film surface with respect to water, as well as suppressing outgassing.

[0398] From the viewpoint of uneven distribution on the film surface, the hydrophobic resin preferably has one or more of the following: fluorine atoms, silicon atoms, and CH3 substructures contained in the side chain portion of the resin, and more preferably two or more. Furthermore, the hydrophobic resin preferably has hydrocarbon groups having 5 or more carbon atoms. These groups may be present in the main chain of the resin or substituted in the side chains. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of International Publication No. 2020 / 004306.

[0399] When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0% by mass, and more preferably 0.1 to 15.0% by mass, relative to the total solid content of the composition.

[0400] <Surfactants> The composition of the present invention may contain a surfactant (E). The inclusion of a surfactant results in superior adhesion and the formation of patterns with fewer development defects. The surfactant is preferably a fluorine-based and / or silicone-based surfactant. Examples of fluorinated and / or silicone-based surfactants include those disclosed in paragraphs

[0218] and

[0219] of International Publication No. 2018 / 193954.

[0401] These surfactants may be used individually or in combination of two or more types.

[0402] If the composition of the present invention contains a surfactant, the surfactant content is preferably 0.0001 to 2.0% by mass, more preferably 0.0005 to 1.0% by mass, and even more preferably 0.1 to 1.0% by mass, relative to the total solid content of the resist composition.

[0403] <Solvent> The composition of the present invention preferably contains a solvent (F). The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0404] The inventors have found that using such solvents in combination with the resins described above improves the coatability of the resist composition and enables the formation of patterns with fewer development defects. Although the reason for this is not entirely clear, the inventors believe that these solvents have a good balance of solubility, boiling point, and viscosity with the resins described above, which suppresses unevenness in the thickness of the resist film and the generation of precipitates during spin coating. Details of components (M1) and (M2) are described in paragraphs

[0218] to

[0226] of International Publication No. 2020 / 004306, and these contents are incorporated herein by reference.

[0405] If the solvent further contains components other than components (M1) and (M2), the content of the components other than components (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of the solvent.

[0406] The solvent content in the composition of the present invention is preferably set so that the solid content concentration is 0.5 to 30% by mass, and more preferably 1 to 20% by mass. This further improves the applicability of the composition of the present invention. Furthermore, "solid content" refers to all components other than the solvent, and as mentioned above, it refers to the components that form a photosensitive or radiation-sensitive film. The solid content concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition of the present invention. "Total solids" refers to the total mass of the components of the composition of the present invention, excluding the solvent. Furthermore, "solids" refers to the components excluding the solvent, as described above, and may be solid or liquid at 25°C, for example.

[0407] <Other additives> The composition of the present invention may further contain a dissolution inhibitor, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a phenol compound with a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

[0408] The composition of the present invention may further contain a dissolution-inhibiting compound. Here, a "dissolution-inhibiting compound" is a compound with a molecular weight of 3000 or less that decomposes due to the action of an acid, thereby reducing its solubility in an organic developer.

[0409] The composition of the present invention is suitably used as a photosensitive composition for EUV light. EUV light has a wavelength of 13.5 nm, which is shorter than ArF light (wavelength 193 nm), resulting in fewer incident photons when exposed at the same sensitivity. Consequently, the "photon shot noise," where the number of photons varies probabilistically, has a greater impact, leading to deterioration of the LER and bridge defects. One way to reduce photon shot noise is to increase the exposure dose to increase the number of incident photons, but this comes at the cost of higher sensitivity.

[0410] [Application] The present invention relates to a photosensitive or radiation-sensitive resin composition whose properties change upon irradiation with active light or radiation. More specifically, the present invention relates to a photosensitive or radiation-sensitive resin composition used in semiconductor manufacturing processes such as ICs (Integrated Circuits), manufacturing of circuit boards such as liquid crystals or thermal heads, fabrication of imprint mold structures, other photofabrication processes, or manufacturing of lithographic printing plates or acid-curable compositions. The patterns formed in the present invention can be used in etching processes, ion implantation processes, bump electrode formation processes, rewiring processes, and MEMS (Micro Electro Mechanical Systems), etc.

[0411] <Method for forming patterns on photosensitive or radiation-sensitive films> The procedure for a pattern formation method using the above composition is not particularly limited, but it is preferable to have the following steps. Step 1: A step of forming an active photosensitive or radiation-sensitive film on a substrate using an active photosensitive or radiation-sensitive resin composition. Step 2: Exposure of a photosensitive or radiation-sensitive film. Step 3: Developing the exposed photosensitive or radiation-sensitive film using a developer. The following details the steps for each of the above processes.

[0412] (Step 1: Actinic ray-sensitive or radiation-sensitive film formation step) Step 1 is a step of forming an active photosensitive or radiation-sensitive film on a substrate using the composition of the present invention.

[0413] One method for forming an activated light-sensitive or radiation-sensitive film on a substrate using an activated light-sensitive or radiation-sensitive resin composition is to apply the activated light-sensitive or radiation-sensitive resin composition onto the substrate. Furthermore, it is preferable to filter the reactive light or radiation-sensitive resin composition before application, if necessary. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0414] The light-sensitive or radiation-sensitive resin composition can be applied to a substrate (e.g., silicon, silicon dioxide coated) used in the manufacture of integrated circuit elements by a suitable coating method such as a spinner or coater. Spin coating using a spinner is preferred. The rotation speed when spin coating using a spinner is preferably 1000 to 3000 rpm. After applying the reactive light or radiation-sensitive resin composition, the substrate may be dried to form a resist film. If necessary, various undercoats (inorganic film, organic film, anti-reflective film) may be formed beneath the resist film.

[0415] As for drying methods, one example is drying by heating. Heating can be carried out using means provided in a normal exposure machine and / or developing machine, or it may be carried out using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0416] The thickness of the light-sensitive or radiation-sensitive film (typically a resist film) is not particularly limited, but 10 to 120 nm is preferred in that it allows for the formation of finer patterns with higher precision. In particular, when using EUV exposure, the film thickness of the reactive light or radiation-sensitive film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. When using ArF immersion exposure, the film thickness of the reactive light or radiation-sensitive film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0417] Furthermore, a topcoat may be formed on the upper layer of the light-sensitive or radiation-sensitive film using a topcoat composition. Preferably, the topcoat composition can be applied uniformly to the surface of the light-sensitive or radiation-sensitive film without being mixed with it. The topcoat is not particularly limited, and conventionally known topcoats can be formed by conventionally known methods. For example, a topcoat can be formed based on the description in paragraphs

[0072] to

[0082] of Japanese Patent Application Publication No. 2014-059543. For example, it is preferable to form a topcoat containing a basic compound, such as that described in Japanese Patent Publication No. 2013-61648, on a light-sensitive or radiation-sensitive film. Specific examples of basic compounds that the topcoat may contain include basic compounds that may be contained in a light-sensitive or radiation-sensitive resin composition. Furthermore, it is preferable that the top coat contains a compound comprising at least one group or bond selected from the group consisting of ether bonds, thioether bonds, hydroxyl groups, thiol groups, carbonyl bonds, and ester bonds.

[0418] (Step 2: Exposure process) Step 2 is the step of exposing the reactive light or radiation-sensitive film. One method of exposure is to irradiate the formed reactive light or radiation-sensitive film with reactive light or radiation through a predetermined mask. Examples of active light or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably with wavelengths of 250 nm or less, more preferably 220 nm or less, and particularly preferably far ultraviolet light with wavelengths of 1 to 200 nm. Specifically, examples include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13 nm), X-rays, and electron beams.

[0419] It is preferable to bake (heat) the image after exposure but before developing. Baking accelerates the reaction in the exposed areas, resulting in better sensitivity and pattern shape. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be performed using the means provided in a standard exposure and / or developing machine, or it may be done using a hot plate or the like. This process is also called post-exposure baking.

[0420] (Process 3: Development process) Step 3 is the process of developing the exposed light-sensitive or radiation-sensitive film using a developer solution to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0421] Examples of development methods include immersing the substrate in a tank filled with developer solution for a certain period of time (dip method), puddling the developer solution onto the substrate surface using surface tension and letting it stand for a certain period of time (paddle method), spraying the developer solution onto the substrate surface (spray method), and continuously dispensing the developer solution while scanning a developer solution dispensing nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispensing method). Alternatively, after the developing process, a step may be performed to stop the development process while substituting with another solvent. The development time is not particularly limited as long as it is enough time for the resin in the unexposed areas to dissolve sufficiently, but 10 to 300 seconds is preferred, and 20 to 120 seconds is more preferred. The temperature of the developer is preferably 0 to 50°C, and more preferably 15 to 35°C.

[0422] It is preferable to use an alkaline aqueous solution containing alkali as the alkaline developer. The type of alkaline aqueous solution is not particularly limited, but examples include alkaline aqueous solutions containing quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. Among these, it is preferable that the alkaline developer be an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, etc., may be added to the alkaline developer. The alkali concentration of the alkaline developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10.0 to 15.0.

[0423] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0424] The above solvents may be mixed in multiple quantities, or mixed with other solvents or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially water-free. The content of the organic solvent in the organic developer is preferably 50% to 100% by mass, more preferably 80% to 100% by mass, even more preferably 90% to 100% by mass, and particularly preferably 95% to 100% by mass, based on the total amount of the developer.

[0425] (Other processes) The above pattern forming method preferably includes a step of washing with a rinsing solution after step 3.

[0426] Examples of rinsing solutions used in the rinsing step after the development process using an alkaline developer include pure water. A suitable amount of surfactant may be added to the pure water. A suitable amount of surfactant may be added to the rinse solution.

[0427] The rinsing solution used in the rinsing step after the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. Preferably, the rinsing solution contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0428] The rinsing process is not particularly limited and can be performed in any way, for example, by continuously discharging rinsing solution onto a substrate rotating at a constant speed (rotary coating method), by immersing the substrate in a tank filled with rinsing solution for a certain period of time (dip method), or by spraying rinsing solution onto the surface of the substrate (spray method). Furthermore, the pattern formation method of the present invention may include a heating step (Post Bake) after the rinsing step. This step removes the developer and rinsing solution remaining between and inside the patterns due to baking. This step also has the effect of softening the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is usually performed at 40 to 250°C (preferably 90 to 200°C) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

[0429] Alternatively, the formed pattern may be used as a mask to perform an etching process on the substrate. In other words, the pattern formed in step 3 may be used as a mask to process the substrate (or the underlying film and the substrate) to form a pattern on the substrate. The processing method for the substrate (or the underlying film and substrate) is not particularly limited, but a preferred method is to form a pattern on the substrate by performing dry etching on the substrate (or the underlying film and substrate) using the pattern formed in step 3 as a mask. Dry etching is preferably performed using oxygen plasma etching.

[0430] The compositions of the present invention and the various materials used in the pattern forming method of the present invention (e.g., solvents, developers, rinses, anti-reflective film forming compositions, topcoat forming compositions, etc.) are preferably free of impurities such as metals. The impurity content in these materials is preferably 1 ppm by mass or less, more preferably 10 ppb by mass or less, even more preferably 100 ppt by mass or less, particularly preferably 10 ppt by mass or less, and most preferably 1 ppt by mass or less. There is no particular lower limit, but 0 ppt by mass or more is preferred. Examples of metallic impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0431] One method for removing impurities such as metals from various materials is filtration using a filter. Details of filtration using a filter are described in paragraph

[0321] of International Publication No. 2020 / 004306.

[0432] Furthermore, methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with low metal content as constituent materials for various materials, filtering the raw materials constituting various materials, and performing distillation under conditions that suppress contamination as much as possible, such as by lining the inside of the apparatus with Teflon®.

[0433] In addition to filter filtration, impurities may be removed using adsorbents, or a combination of filter filtration and adsorbents may be used. Known adsorbents can be used, such as inorganic adsorbents like silica gel and zeolite, and organic adsorbents like activated carbon. To reduce impurities such as metals contained in the above materials, it is necessary to prevent the introduction of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components in the cleaning solution used to clean the equipment. The content of metal components in the cleaning solution after use is preferably 100 ppt (parts per trillion) or less, more preferably 10 ppt or less, and even more preferably 1 ppt or less. There is no particular lower limit, but 0 ppt or more is preferred.

[0434] In organic processing solutions such as rinsing solutions, a conductive compound may be added to prevent malfunctions of chemical piping and various parts (filters, O-rings, and tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge. The conductive compound is not particularly limited, but methanol is an example. The amount added is not particularly limited, but in terms of maintaining desirable developing or rinsing characteristics, 10% by mass or less is preferred, and 5% by mass or less is more preferred. There is no particular lower limit, but 0.01% by mass or more is preferred. For chemical piping, various types of piping can be used, such as SUS (stainless steel), or piping coated with antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.). Similarly, for filters and O-rings, antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) can be used.

[0435] <Method of manufacturing electronic devices> Furthermore, the present invention relates to a method for manufacturing an electronic device, including the pattern formation method described above, and to an electronic device manufactured by this manufacturing method. Preferred embodiments of the electronic device of the present invention include those mounted on electrical and electronic equipment (such as home appliances, office automation equipment, media-related equipment, optical equipment, and communication equipment). [Examples]

[0436] The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below.

[0437] <Resin (A)> The structure of the repeating units of the resin (A) used, its composition ratio (mol% ratio), weight-average molecular weight (Mw), and degree of dispersion (Mw / Mn) are shown below. The composition ratio (molar percentage; corresponding from left to right), weight-average molecular weight (Mw), and degree of dispersion (Mw / Mn) of each repeating unit in the resin (A) used are also shown. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of resin (A) were measured by GPC (solvent: tetrahydrofuran (THF)). The composition ratio (mol% ratio) of the resin was also determined as follows: 13 The measurement was performed using 1C-NMR (nuclear magnetic resonance).

[0438] [ka]

[0439] <Compound (I)> (Synthesis Example 1) Synthesis of Compound X-1

[0440] [ka]

[0441] In a 300 mL three-necked flask, 10.0 g (22.9 mmol) of compound (X-1-A), 100 mL of acetonitrile, and 5.9 g (45.7 mmol) of diisopropylethylamine were added and cooled to 0°C. Then, 8.7 g (22.9 mmol) of compound (X-1-B) was slowly added, and the reaction was carried out for 2 hours. After removing the aqueous layer by adding 200 mL of methylene chloride and 100 mL of water, the organic phase was washed twice with 100 mL of water, and the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography (elution with a chloroform / methanol mixed solvent) to obtain 11.6 g of compound (X-1) as a white solid (yield 70%). 1 H-NMR (300MHz, heavy DMSO): δ (ppm) 7.81 (m, 29H) 19 F-NMR (300MHz, heavy DMSO): δ(ppm) -109.03(2F)

[0442] (Synthesis Example 2) Synthesis of Compound X-8

[0443] [ka]

[0444] In a 300 mL three-necked flask, 10.0 g (17.4 mmol) of compound (X-8-A), 100 mL of acetonitrile, and 4.5 g (34.9 mmol) of diisopropylethylamine were added and cooled to 0°C. Then, 6.6 g (22.9 mmol) of compound (X-8-B) was slowly added, and the reaction was carried out for 2 hours. After removing the aqueous phase by adding 200 mL of methylene chloride and 100 mL of water, the organic phase was washed twice with 100 mL of water, and the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography (elution with a chloroform / methanol mixed solvent) to obtain 10.4 g of compound (X-8) as a white solid (yield 68%). 1 H-NMR (300MHz, heavy DMSO): δ(ppm) 6.81(d,1H),7.66(m,4H),7.83(m,16H),8.29(m,3H) 19F-NMR (300MHz, heavy DMSO): δ(ppm) -118.69(2F),-114.11(2F),-113.13(2F)

[0445] Compounds (X-2) to (X-7) and compounds (X-9) to (X-16) were synthesized in the same manner as in Synthesis Example 1 and Synthesis Example 2 described above. The structures of compounds (X-1) to (X-16) are shown below.

[0446] [ka]

[0447] [ka]

[0448] (Acid dissociation constant pKa of the acid generated from compound (I)) Table 1 shows the acid dissociation constants pKa of the acid generated from compound (I). In measuring the acid dissociation constant pKa of the acid generated from compound (I), specifically, for compounds obtained by replacing each acid anionic group in compounds X-1 to X-16 with each acid group, the values ​​were calculated using Hammett substituent constants and a database of publicly available literature values, as described above, using ACD / Labs' software package 1. Furthermore, if the pKa could not be calculated using the above method, the value obtained by Gaussian16 based on DFT (density functional theory) was adopted. In the table below, "pKa1" represents the acid dissociation constant for the first stage, "pKa2" represents the acid dissociation constant for the second stage, and "pKa3" represents the acid dissociation constant for the third stage. A smaller pKa value indicates higher acidity.

[0449] As described above, compounds X-1 to X-3 and X-5 to X-16 correspond to compound (I) mentioned above. Here, pKa1 corresponds to the acid dissociation constant a1 mentioned above, and pKa2 corresponds to the acid dissociation constant a2 mentioned above.

[0450] Furthermore, as mentioned above, compound X-4 also corresponds to compound (I) described above. Here, pKa1 corresponds to the acid dissociation constant a1 described above, pKa2 corresponds to the acid dissociation constant a2 described above, and pKa3 corresponds to the acid dissociation constant a3 described above. Acid generated from compound X-4 (the two sulfonium cations of compound X-4 are converted to H + Replace with one CO2 - H + Since the compound formed by adding () has a symmetric structure, the acid dissociation constants pKa of the acid groups derived from the two acid anionic groups are theoretically the same. For convenience, two pKa values ​​with the same value are denoted as "pKa1" and "pKa2," respectively, and a higher pKa value is denoted as "pKa3."

[0451] [Table 1]

[0452] In Table 1, the number of linked ions indicates the number of cationic groups and anionic groups in the chain in which at least one acid anionic group and at least one cationic group in compound (I) are covalently linked.

[0453] <Photoacid Generator (B)> The structure of a photoacid generator that does not correspond to compound (I) used is shown below.

[0454] [ka]

[0455] <Acid diffusion control agent> The structure of the acid diffusion control agent used is shown below.

[0456] [ka]

[0457] <Hydrophobic resin> The structure of the repeating units of the hydrophobic resin used, their composition ratio (mol% ratio), weight-average molecular weight (Mw), and degree of dispersion (Mw / Mn) are shown below. The composition ratio (mol% ratio; corresponding from left to right), weight-average molecular weight (Mw), and degree of dispersion (Mw / Mn) of each repeating unit in the hydrophobic resin used are also shown. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of resin (A) were measured by GPC (solvent: tetrahydrofuran (THF)). The composition ratio (mol% ratio) of the resin was also determined as follows: 13 The measurement was performed using 1C-NMR (nuclear magnetic resonance).

[0458] [ka]

[0459] <Surfactants> As the surfactant, E-1 was used. E-1: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based)

[0460] <Solvent> The solvents used are listed below. F-1: Propylene glycol monomethyl ether acetate (PGMEA: 1-Methoxy-2-acetoxypropane) F-2: Propylene glycol monomethyl ether (PGME: 1-methoxy-2-propanol) F-3: Cyclohexanone F-4: γ-Butyrolactone F-5: Ethyl lactate

[0461] (Examples 1-1 to 1-21, 2-1 to 2-21, 3-1 to 3-14, 4-1 to 4-14, Comparative Examples 1-1 to 1-3, 2-1 to 2-3, 3-1 to 3-3, 4-1 to 4-3) <Preparation of Resist Composition> (ArF Exposure) (Examples 1-1 to 1-21, 2-1 to 2-21, Comparative Examples 1-1 to 1-3, 2-1 to 2-3) The components shown in Table 2 were dissolved in the solvents shown in Table 2 to prepare a solution with a solid content concentration of 4.0% by mass. This solution was then filtered through a polyethylene filter with a pore size of 0.02 μm to prepare a resist composition. Note that "solid content" refers to all components other than the solvent. The obtained resist composition was used in the examples and comparative examples. In the table, the "mass%" column indicates the content (mass%) of each component relative to the total solids in the resist composition. The table also shows the amount (parts by mass) of the solvent used.

[0462] <Pattern formation method (1): ArF exposure, alkaline development (positive)> The resist compositions shown in Table 2, immediately after manufacturing, were coated onto a 6-inch Si wafer that had been pre-treated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark8 spin coater. The wafers were then dried on a hot plate at 100°C for 60 seconds to obtain a resist film with a thickness of 90 nm. Here, 1 inch is equal to 0.0254 m. A wafer with a resist film formed on it was pattern-exposed using an ArF excimer laser scanner (ASML, PAS5500 / 1500, wavelength 193 nm, NA 0.50) through an exposure mask. Afterward, it was baked at 115°C for 60 seconds, developed with 2.38 mass% tetramethylammonium hydroxide aqueous solution (TMAHaq) for 30 seconds, rinsed with pure water, and then spin-dried. This yielded a resist pattern with a 1:1 line-and-space pattern and a line width of 50 nm.

[0463] <Performance Evaluation> [Storage stability] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (SEM, Hitachi, Ltd., S-9380II). The exposure dose required to resolve a 1:1 line-and-space resist pattern with a line width of 50 nm was defined as the sensitivity (Eop). After storing the resist composition at room temperature (23°C) for one month, a 1:1 line-and-space pattern with a line width of 50 nm was formed following the same procedure as described above. The exposure amount required to resolve this resist pattern was defined as the sensitivity (Eop). The difference in sensitivity {|(exposure required to resolve the pattern using the composition stored at room temperature for one month - exposure required to resolve the pattern using the composition immediately after manufacturing)|} between using a composition immediately after manufacturing and a composition that had been stored at room temperature for one month after manufacturing was evaluated according to the following criteria. A: The difference in sensitivity is 1 mJ / cm 2 It is less than. B: The difference in sensitivity is 1 mJ / cm 2 More than 3mJ / cm 2 It is less than. C: Sensitivity difference is 3 mJ / cm 2 That's all.

[0464] [Pattern Shape] Cross-sections of 1:1 line-and-space patterns with a line width of 50 nm were observed using a scanning electron microscope (SEM, Hitachi, Ltd., S-9380II). The pattern line width Lb at the bottom of the resist pattern and the pattern line width La at the top of the resist pattern were measured, and the pattern shape was evaluated on a four-point scale: A, B, C, and D. A: (Lb / La) ≤ 1.03 B: 1.03 < (Lb / La) ≤ 1.06 C:1.06<(Lb / La)≦1.1 D:1.1<(Lb / La)

[0465] <Pattern formation method (2): ArF exposure, alkaline development (negative)> The resist compositions shown in Table 2, immediately after manufacturing, were coated onto a 6-inch Si wafer that had been pre-treated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark8 spin coater. The wafers were then dried on a hot plate at 100°C for 60 seconds to obtain a resist film with a thickness of 90 nm. Here, 1 inch is equal to 0.0254 m. A wafer with a resist film formed on it was pattern-exposed using an ArF excimer laser scanner (ASML, PAS5500 / 1500, wavelength 193 nm, NA 0.50) through an exposure mask. Afterward, it was baked at 115°C for 60 seconds, developed with n-butyl acetate for 30 seconds, and spin-dried. This yielded a resist pattern with a 1:1 line-and-space pattern and a line width of 50 nm.

[0466] <Performance Evaluation> [Storage stability] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (SEM, Hitachi, Ltd., S-9380II). The exposure dose required to resolve a 1:1 line-and-space resist pattern with a line width of 50 nm was defined as the sensitivity (Eop). After storing the resist composition at room temperature (23°C) for one month, a 1:1 line-and-space pattern with a line width of 50 nm was formed following the same procedure as described above. The exposure amount required to resolve this resist pattern was defined as the sensitivity (Eop). The difference in sensitivity {|(exposure amount required to resolve the pattern using the composition stored at room temperature for one month - exposure amount required to resolve the pattern using the composition immediately after manufacturing)|} between using a composition immediately after manufacturing and a composition stored at room temperature for one month after manufacturing was evaluated according to the following criteria. A: The difference in sensitivity is 1 mJ / cm 2 It is less than. B: The difference in sensitivity is 1 mJ / cm 2 More than 3mJ / cm 2 It is less than. C: Sensitivity difference is 3 mJ / cm 2 That's all.

[0467] [Pattern Shape] Cross-sections of 1:1 line-and-space patterns with a line width of 50 nm were observed using a scanning electron microscope (SEM, Hitachi, Ltd., S-9380II). The pattern line width Lb at the bottom of the resist pattern and the pattern line width La at the top of the resist pattern were measured, and the pattern shape was evaluated on a four-point scale: A, B, C, and D. A: (Lb / La) ≤ 1.03 B: 1.03 < (Lb / La) ≤ 1.06 C:1.06<(Lb / La)≦1.1 D:1.1<(Lb / La)

[0468] <Preparation of Resist Composition> (EUV Exposure) (Examples 3-1 to 3-14, 4-1 to 4-14, Comparative Examples 3-1 to 3-3, 4-1 to 4-4) The components shown in Table 3 were dissolved in the solvents shown in Table 3 to prepare a solution with a solid content concentration of 2.0% by mass. This solution was then filtered through a polyethylene filter having a pore size of 0.02 μm to prepare a resist composition. Note that "solid content" refers to all components other than the solvent. The obtained resist composition was used in the examples and comparative examples. In the table, the "mass%" column indicates the content (mass%) of each component relative to the total solids in the resist composition. The table also shows the amount (parts by mass) of the solvent used.

[0469] <Pattern formation method (3): EUV exposure, alkaline development (positive)> A base layer film formation composition AL412 (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form a 20 nm thick base layer. On top of this, the immediately manufactured resist composition shown in Table 3 was applied and baked at 100°C for 60 seconds to form a 30 nm thick resist film. A silicon wafer with a resist film obtained was patterned using an EUV lithography system (Exitech Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36). A mask with a line size of 50 nm and a line-to-space ratio of 1:1 was used as the reticle. The resist film after exposure was baked at 90°C for 60 seconds, then developed with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 30 seconds, followed by rinsing with pure water for 30 seconds. This was then spin-dried to obtain a resist pattern with a 1:1 line-and-space pattern and a line width of 50 nm.

[0470] <Performance Evaluation> [Storage stability] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (SEM, Hitachi, Ltd., S-9380II). The exposure dose required to resolve a 1:1 line-and-space resist pattern with a line width of 50 nm was defined as the sensitivity (Eop). After storing the resist composition at room temperature (23°C) for one month, a 1:1 line-and-space pattern with a line width of 50 nm was formed following the same procedure as described above. The exposure amount required to resolve this resist pattern was defined as the sensitivity (Eop). The difference in sensitivity {|(exposure amount required to resolve the pattern using the composition stored at room temperature for one month - exposure amount required to resolve the pattern using the composition immediately after manufacturing)|} between using a composition immediately after manufacturing and a composition stored at room temperature for one month after manufacturing was evaluated according to the following criteria. A: The difference in sensitivity is 1 mJ / cm 2 It is less than. B: The difference in sensitivity is 1 mJ / cm 2 More than 3mJ / cm 2 It is less than. C: Sensitivity difference is 3 mJ / cm 2 That's all.

[0471] [Pattern Shape] Cross-sections of 1:1 line-and-space patterns with a line width of 50 nm were observed using a scanning electron microscope (SEM, Hitachi, Ltd., S-9380II). The pattern line width Lb at the bottom of the resist pattern and the pattern line width La at the top of the resist pattern were measured, and the pattern shape was evaluated on a four-point scale: A, B, C, and D. A: (Lb / La) ≤ 1.03 B: 1.03 < (Lb / La) ≤ 1.06 C:1.06<(Lb / La)≦1.1 D:1.1<(Lb / La)

[0472] <Pattern formation method (4): EUV exposure, organic solvent development (negative)> A base layer film formation composition AL412 (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form a 20 nm thick base layer. On top of this, the immediately manufactured resist composition shown in Table 3 was applied and baked at 100°C for 60 seconds to form a 30 nm thick resist film. A silicon wafer with a resist film obtained was patterned using an EUV lithography system (Exitech Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36). A mask with a line size of 50 nm and a line-to-space ratio of 1:1 was used as the reticle. After exposure, the resist film was baked at 90°C for 60 seconds, then developed with n-butyl acetate for 30 seconds, and spin-dried to obtain a 1:1 line-and-space pattern resist with a line width of 50 nm.

[0473] <Performance Evaluation> [Storage stability] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (SEM, Hitachi, Ltd., S-9380II). The exposure dose required to resolve a 1:1 line-and-space resist pattern with a line width of 50 nm was defined as the sensitivity (Eop). After storing the resist composition at room temperature (23°C) for one month, a 1:1 line-and-space pattern with a line width of 50 nm was formed following the same procedure as described above. The exposure amount required to resolve this resist pattern was defined as the sensitivity (Eop). The difference in sensitivity {|(exposure amount required to resolve the pattern using the composition stored at room temperature for one month - exposure amount required to resolve the pattern using the composition immediately after manufacturing)|} between using a composition immediately after manufacturing and a composition stored at room temperature for one month after manufacturing was evaluated according to the following criteria. A: The difference in sensitivity is 1 mJ / cm 2 It is less than. B: The difference in sensitivity is 1 mJ / cm 2 More than 3mJ / cm 2 It is less than. C: Sensitivity difference is 3 mJ / cm 2 That's all.

[0474] [Pattern Shape] Cross-sections of 1:1 line-and-space patterns with a line width of 50 nm were observed using a scanning electron microscope (SEM, Hitachi, Ltd., S-9380II). The pattern line width Lb at the bottom of the resist pattern and the pattern line width La at the top of the resist pattern were measured, and the pattern shape was evaluated on a four-point scale: A, B, C, and D. A: (Lb / La) ≤ 1.03 B: 1.03 < (Lb / La) ≤ 1.06 C:1.06<(Lb / La)≦1.1 D:1.1<(Lb / La)

[0475] The evaluation results obtained are shown in Tables 2 and 3.

[0476] [Table 2-1]

[0477] [Table 2-2]

[0478] [Table 3-1]

[0479] [Table 3-2]

[0480] As shown in Tables 2 and 3 above, the resist composition of the present invention exhibits excellent storage stability and, when a fine pattern is formed by alkaline development or organic solvent development, it was confirmed to produce an excellent pattern shape. On the other hand, the resist compositions of the comparative examples exhibited insufficient performance in these areas.

Claims

1. A photosensitive or radiation-sensitive resin composition containing a compound (I) that generates acid upon irradiation with active light or radiation, The compound (I) has two or more acid anionic groups and the same number of cationic groups as the acid anionic groups, At least one of the acid anionic groups and at least one of the cationic groups are linked via a covalent bond. The two or more acid groups generated in compound (I) by irradiation with active light or radiation include at least two acid groups with different acid dissociation constants (pKa). A photosensitive or radiation-sensitive resin composition in which the compound (I) is a compound represented by any of the following general formulas (I)-1 to (I)-5. 【Chemistry 1】 In general formulas (I)-1 to (I)-5, A11- to A20- each independently represent an acid anionic group. C¹¹+, C¹³+ to C¹⁴+, C¹⁶+, and C¹⁸+ each independently represent a cationic group. C12+, C15+, C17+, C19+, and C20+ each independently represent a group represented by the following formula (ZBI) or formula (ZBII). L11 to L14 and L16 to L21 each independently represent a divalent organic group. L 15 represents a trivalent organic group. 【Chemistry 2】 In equations (ZBI) and (ZBII), R 301, R 302, and R 303 each independently represent an aryl group, an alkyl group, or a cycloalkyl group. R 301 to R 302 may bond together to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. * indicates the joining position.

2. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein the compound (I) is a compound in which one cationic group and two acid anionic groups are linked by a covalent bond.

3. The photosensitive or radiation-sensitive resin composition according to claim 1, wherein compound (I) is a compound in which all of the acid anionic groups and all of the cationic groups are linked via covalent bonds.

4. A in the above general formulas (I)-1 to (I)-5 １１ － A １３ － ~A １６ － A １８ － The photosensitive or radiation-sensitive resin composition according to claim 1, wherein each independently represents an acid anionic group represented by the following formula (A-1) or (A-2). 【Transformation 3】 In the above formulas (A-1) to (A-2), R Ａ represents an organic group. * indicates the joining position.

5. In the above general formulas (I)-1, (I)-4 and (I)-5, A １２ － A １７ － A １９ － A ２０ － The photosensitive or radiation-sensitive resin composition according to claim 1, wherein each independently represents an acid anionic group represented by any of the following formulas (B-1) to (B-3). 【Chemistry 4】 In the above formulas (B-1) to (B-3), * indicates the joining position.

6. The photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the difference between the maximum and minimum pKa values ​​of the pKa of two or more acid groups generated by irradiation of the compound (I) by active light or radiation is 1.60 or more.

7. The photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the compound (I) is a compound having an ionic structure in which a pair of one acid anionic group and one cationic group are linked via an ionic bond.

8. A photosensitive or radiation-sensitive resin composition containing a compound (I) that generates acid upon irradiation with active light or radiation, The compound (I) has two or more acid anionic groups and the same number of cationic groups as the acid anionic groups, At least one of the acid anionic groups and at least one of the cationic groups are linked via a covalent bond. Two or more acid anionic groups of compound (I) include two or more anionic groups selected from the group consisting of the following formulas (C-1) to (C-15). The compound (I) is a compound represented by any of the following general formulas (II)-1 to (II)-5. Actinic ray-sensitive or radiation-sensitive resin composition. 【Transformation 5】 In the general formulas (C-1) to (C-15), * indicates the joining position. Rf １ ~Rf ８ Each of these independently represents a fluorine atom or a monovalent substituent containing one or more fluorine atoms. Rf ９ This represents a perfluoroalkyl group. R １ ~R ７ Each of these independently represents a monovalent substituent that does not contain a hydrogen atom or a fluorine atom. Ar １ ~Ar ４ Each of these independently represents an aromatic ring. 【Transformation 6】 In general formula (II)-1, A 111- represents a group represented by any of the above formulas (C-1) to (C-12). A 112 - represents a group represented by any of the above formulas (C-13) to (C-15). C111+ to C112+ each independently represent a cationic group. L 111 to L 112 each independently represent a single bond or a divalent organic group. In general formula (II)-2, A113- and A114- each independently represent a base represented by any of the above formulas (C-1) to (C-12). A13- and A14- are not identical. C113+ to C114+ each independently represent a cationic group. L 113 to L 114 each independently represent a single bond or a divalent organic group. In general formula (II)-3, A115- and A116- each independently represent a base represented by any of the above formulas (C-1) to (C-12). A115- and A116- are not identical. C115+ to C116+ each independently represent a cationic group. L 115 represents a trivalent organic group. In general formula (II)-4, A 117- represents a group represented by any of the above formulas (C-13) to (C-15). A 118 - represents a group represented by any of the above formulas (C-1) to (C-12). C117+ to C118+ each independently represent a cationic group. L 116 to L 118 each independently represent a single bond or a divalent organic group. In general formula (II)-5, A119- and A120- each independently represent a group represented by any of the above formulas (C-3) to (C-15). A119- and A120- are not identical. C119+ to C120+ each independently represent a cationic group. L 119 to L 121 each independently represent a single bond or a divalent organic group.

9. A photosensitive or radiation-sensitive film formed from a photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 5 and 8.

10. A step of forming an active photosensitive or radiation-sensitive film on a substrate using the active photosensitive or radiation-sensitive resin composition according to any one of claims 1 to 5 and 8, A step of exposing the aforementioned photosensitive or radiation-sensitive film, A step of developing the exposed photosensitive or radiation-sensitive film using a developer, A pattern forming method having the following characteristics.

11. A method for manufacturing an electronic device, comprising the pattern formation method described in claim 10.

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